RU2275238C1 - Photochemical reaction catalyst in the form of titanium dioxide-based mesoporous material and a method for preparation thereof - Google Patents

Abstract

FIELD: catalyst preparation methods.

SUBSTANCE: catalyst containing crystalline anatase phase in amount at least 30% and nickel in amount 0.5 to 2% has porous structure with mean pore diameter 2 to 16 nm and specific surface at least 70 m²/g. When used to catalyze photochemical reaction of isolation of hydrogen from water-alcohol mixtures, it provides quantum yield of reaction 0.09-0.13. Preparation of titanium dioxide-based mesoporous material comprises adding titanium tetraalkoxide precursor and organic-nature template to aqueous-organic solvent, ageing reaction mixture to complete formation of spatial structure therefrom through consecutive sol and gel formation stages, separating reaction product, and processing it to remove template. Invention is characterized by that water-alcohol derivative contains no more than 7% water and template consists of at least one ligand selected from group of macrocyclic compounds, in particular oxa- and oxaazamacrocyclic compounds containing at least four oxygen atoms, and/or complexes of indicated macrocyclic compounds with metal ions selected from group of alkali metals or alkali-earth metal metals, or f-metals consisting, in particular, of lithium, potassium, sodium, rubidium, cesium, magnesium, calcium, strontium, barium, lanthanum, and cerium used in amounts from 0.001 to 0.2 mole per 1 mole precursor. Sol is formed by stirring reaction mixture at temperature not higher than 35°C. Once formation of spaced structure completed, mixture is held at the same temperature in open vessel to allow free access of water steam and, when template is removed from the mixture, mixture is first treated with nickel salt solution and then with alkali metal borohydride solution until metallic nickel is formed.

EFFECT: increased sorption and photocatalytic properties of catalyst and enabled reproducibility of its property complex.

7 cl, 68 ex

Description

Technical field

The invention relates to the composition and structure of composite metal-semiconductor mesoporous materials based on titanium dioxide and to methods for producing such materials.

Such composite metal-containing mesoporous materials without additional involvement of catalysts of the "dark" stages of reactions 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 purifying, for example, air and industrial effluents from harmful organic compounds by heterogeneous photocatalytic oxidation of these compounds 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;

the catalyst for the dark stage of the reaction is a metal that does not directly participate in the primary acts of the photochemical process, but has the ability to accelerate the secondary, "dark" (not requiring the use of radiation) process stages;

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, such as hydrolysis, becomes a source of material for the formation of a framework of a porous dispersed material on a template during the 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, in 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 photochemical reactions of molecular hydrogen evolution or, for example, as sorbents-catalysts of heterogeneous photochemical processes of oxidation of organic compounds should provide:

the highest quantum yields of product formation reactions (i.e., should have the highest possible efficiency);

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

In addition, such materials should be affordable, and the resource of their work should be long.

In turn, methods for producing such dispersed materials based on titanium dioxide should be simple and should include the use of generally available reagents. At the same time, such methods should provide stable reproducibility of the properties of the final products.

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

Thus, 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.html). 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 / Edited by M. Grettsel. - M .: Mir, 1986. - P.364): when photons are absorbed by them, electrons are excited in the conduction band, and holes are generated in the valence band, respectively taking part in molecular reduction and oxidation reactions 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 fairly high quantum yields of hydrogen formation (about 0.4), provided that the very expensive platinum or palladium dark catalyst is additionally used stages of these reactions, which are usually applied to a single finely divided inert carrier, for example, silica gel and the role of which is known (see, for example, Balzani V. , Scandola F., Infelt P. et al. Energy resources through the prism of photochemistry and catalysis: Translated from English / Edited by M. Gretzel. - M .: Mir, 1986. - P.365), consists in the accumulation of the resulting as a result of the reaction of atomic hydrogen and its conversion 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. In addition, for the effective functioning of this material as a photocatalyst for the production of molecular hydrogen, intensive mixing with a finely dispersed metal catalyst of the dark stage of the reaction is necessary, since only close contact of the particles of the semiconductor photocatalyst and the grains of the carrier with the dark catalyst promotes the separation of charges photogenerated in the semiconductor and the accumulation on a metal of photogenerated electrons, the discharge of a protonated molecule water on the metal surface recombination formed hydrogen atoms and molecular hydrogen desorption (ibid.).

Obviously, as a result of the forced use of a finely dispersed support of a metal catalyst in the mixing mode, a significant part of the light radiation directed into the reactor is scattered and does not reach the photocatalyst. It is also obvious that the consequence of intensive mixing of the reaction mixture is the gradual abrasive wear of both the particles of the photocatalyst and the particles of the catalyst carrier of the dark reaction stage with the loss, in particular, of a very expensive precious metal.

A method of obtaining a crystalline modification of titanium dioxide - anatase, which is mainly Degussa P 25 material, is well known (see, for example, Manual on Inorganic Synthesis. Edited by G. Brauer. - M .: Mir, 1985. - T.4 - C .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 known method is relatively simple and, in addition, provides an 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.

Also known is a mesoporous material based on titanium dioxide having 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 material has a high sorption capacity. Therefore, it can be a good concentrator of vapors of organic compounds that are subject to subsequent decomposition.

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

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

This method allows to obtain sorption-active material based on 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 a mesoporous material based on titanium dioxide with photocatalytic properties.

The closest in technical essence and the achieved effect to the claimed group of objects are mesoporous material based on titanium dioxide and the method 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, and a prototype process for obtaining such material is described in stages, indicating the conditions for each stage of the synthesis. In the second (by other authors), the photocatalytic properties of the prototype material were studied and the nature of its photocatalytic activity was explained.

Known Mesoporous Material Based on 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 vapor concentrator of organic compounds.

However, this mesoporous material based on titanium dioxide is characterized by a rather low quantum yield of molecular hydrogen production (not more than 0.01), provided that the platinum or palladium catalyst is additionally used in the dark stage of the reaction (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 photocatalytically inactive amorphous material titanium dioxide phases (see ibid., p. 1471, figure 4). In addition, the decrease in the photocatalytic activity of the known material is also facilitated by the content in its pores of a template fragment - phosphorus (see ibid.). Therefore, this mesoporous material based on titanium dioxide is not effective enough as a sorbent photocatalyst in terms of its set of properties.

A method for producing a known titanium dioxide-based mesoporous material includes (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) dissolution in water of a template - monododecylphosphate and a potassium pH hydroxide regulator, dissolution of a precursor in the form of tetraalkoxide (isopropoxide) titanium in an organic solvent - acetylacetone, mixing the resulting solutions, holding the mixture at temperature about 80 ° C in a vessel isolated from the external environment until the formation of prostra natural structure, which, as you know, includes the intermediate stages of the formation of a sol and then a gel (see, for example, 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 a mesoporous material based on 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 a mesoporous material based on 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).

SUMMARY OF THE INVENTION

The basis of the group of inventions is the task, by improving the composition and texture of a mesoporous material based on titanium dioxide, to create a composite metal-semiconductor mesoporous material based on titanium dioxide with high sorption and photocatalytic characteristics and by selecting reagents for implementing the method of producing such a mesoporous material and synthesis conditions to ensure reproducibility the set of properties of such a sorbent-photocatalyst.

The problem is solved in that the mesoporous material based on titanium dioxide according to the invention contains a crystalline anatase phase in an amount of at least 30 wt.%, Nickel in an amount of from 0.5 to 2 wt.%, Has a porous structure with an average pore diameter of from 2 to 16 nm, a specific surface area of not less than 70 m ² / g and, as a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, provides a quantum yield of the reaction from 0.09 to 0.13.

The first additional difference is that it additionally contains lanthanum in an amount of not more than 0.019 grams per gram of titanium dioxide contained in the material.

The problem is also solved by the fact that in the method for producing a mesoporous material based on titanium dioxide, which includes introducing a precursor tetraalkoxide of titanium and a template of organic nature into an aqueous organic solvent, holding the mixture of reagents to the final formation of the spatial structure from it through the successive stages of sol formation, and then 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, with containing not more than 7 wt.% water, 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 is introduced into the solvent as a template compounds with metal ions selected from the group of alkali, or alkaline earth, or f-metals, consisting of lithium, potassium, sodium, rubidium, cesium, magnesium, calcium, strontium, barium, lanthanum and cerium, until the formation of a sol, the mixture of reagents they are sewn, maintaining its temperature no higher than 35 ° С, until the final formation of the spatial structure of the reagents from the mixture, the mixture is kept at the same temperature in an open vessel under free access to a mixture of water vapor and, after removal from the spatial structure, the template is first treated with a solution of nickel salt, and then with an alkali metal borohydride solution to form metallic nickel.

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.

BEST EMBODIMENTS

Further, the essence of the group of inventions is illustrated by generalized examples of a method for producing a mesoporous material based on titanium dioxide, methods for determining the parameters of the porous structure of the final product (composite metal-semiconductor mesoporous material based on titanium dioxide), methods for determining the phase composition of the final product and methods for assessing the photocatalytic properties of the finished product on An example of its use as a catalyst for the photochemical reaction of the release of molecular hydrogen from water but-alcohol mixtures.

The essence of the group of inventions is also illustrated by specific examples of a method for producing a mesoporous material based on titanium dioxide, which shows the parameters of the porous structure, composition and photocatalytic properties of the obtained composite metal-semiconductor mesoporous material based on titanium dioxide that are determined by these methods (without repeated reference to them).

Example 1. A generalized method for producing a mesoporous material based on titanium dioxide, generalized methods for determining the parameters of the porous structure, composition and photocatalytic properties of the mesoporous material based on titanium dioxide.

At least one of the oxa or oxazamacrocyclic compounds (e.g. tetramethyl-12-corona-4 of the general formula C ₁₂ H ₂₄ O ₄ , dibenzo-18-corona-6 of the general of the formula C ₂₀ H ₂₄ O ₆ , 18-Coronaase-2-oxa-4 of the general formula C ₁₂ H ₂₆ O ₄ N ₂ , 18-Coronaase-1-oxa-5 of the general formula C ₁₂ H ₂₅ O ₅ N) containing no less than four oxygen atoms (preferably not more than ten) and / or one of the complexes of these macrocyclic compounds with an alkaline ion (lithium, sodium, s, rubidium, cesium) or alkaline earth (magnesium, calcium, strontium, barium), or f-metal (lanthanum, cerium), e.g., complex oksamakrotsiklicheskogo compounds tetramethyl-12-crown-4 with lithium ion of the general formula [Li (C ₁₂ H ₂₄ O ₄ )] Cl · 3H ₂ O, complexes of the same oxamacrocyclic compound with a barium ion of the general formula [Ba (C ₁₂ H ₂₄ O ₄ )] Cl ₂ · 3H ₂ O and with a cerium ion of the general formula [Ce (C ₁₂ H ₂₄ O ₄ )] Cl ₃ · 3H ₂ O or a complex of the oxazazamacrocyclic compound 18-Coronaase-2-oxa-4 with a sodium ion of the general formula [Na (C ₁₂ H ₂₆ O ₄ N ₂ )] Cl · 3H ₂ O, complexes of the same oxazazamacrocyclic compound tendency with a rubidium ion of the general formula [Rb (C ₁₂ H ₂₆ O ₄ N ₂ )] Br · 3H ₂ O, with a magnesium ion of the general formula [Mg (C ₁₂ H ₂₆ O ₄ N ₂ )] SO ₄ · 3H ₂ O and with a lanthanum ion of the general formula [La (C ₁₂ H ₂₆ O ₄ N ₂ )] Cl ₃ · ₇ H ₂ O. Note that the organic templates are in the form of oxo and oxazamacrocyclic compounds, as well as complexes of these compounds with the listed metals that 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 a mesoporous material based on 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 a mesoporous material based on titanium dioxide. As the experiments of the nation have shown, other alcohols can be used 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.

Before the synthesis of the mesoporous material based on 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 to synthesize a mesoporous material based on titanium dioxide was one of the oxa or oxazamacrocyclic compounds or a complex of one of such macrocyclic compounds that does not contain a lanthanum ion, a salt was introduced in addition to the template in addition to the template lanthanum in an amount of 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, Vol. 1, P.513) - spontaneous final compaction of the spatial structure of titanium dioxide / template and, as a result , stopping the displacement of the liquid phase from it.

For each mixture of specific reagents (precursor, organic template, and water-alcohol solvent) taken separately for the synthesis of mesoporous material, the time of the final formation of the spatial structure of the titanium dioxide / organic template composition from it was determined experimentally for different synthesis conditions.

It was found that increasing the temperature of the reaction mixture above the specified limit (35 ° C) at such stages of the synthesis of the mesoporous material 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 and, first of all, contributes to the formation of a product with a small specific surface area. The lower experimentally established temperature limit at which these stages of the synthesis of mesoporous material should be carried out is 10 ° С. 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 methods for removing the template (by calcination or extraction with alcohol) from the spatial structure finally formed from the reagent mixture and the procedure for obtaining the required amount of photocatalytically active anatase in the material, 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 the material, calcination was used, the structure was previously separated by filtration from the mother liquor, dried in air until the solvent was almost completely removed from it, and then crushed in the 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 production of mesoporous titanium dioxide was the achievement of the contents of the crucible with 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 its contents after cooling. As shown by the results of x-ray phase analysis of 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 mesoporous material decreased markedly and it was not possible to obtain such a material 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 the mesopores in the material to micropore sizes.

In some cases, before calcining the finally formed spatial structure, titanium dioxide / template was subjected to hydrothermal treatment at a temperature of 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 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 the material, which began 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 a mesoporous material 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, was necessarily 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 the mesoporous material.

After this preliminary hydrothermal treatment, the mother liquor structure was removed from the autoclave. The structure was separated by filtration from the mother liquor, dried until the solvent was almost completely removed, and then crushed in a dispersant. The resulting structure powder was placed in a glass beaker. With vigorous stirring, alcohol, predominantly ethyl alcohol, was added to the glass, 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 / 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.

Mesoporous titanium dioxide obtained by one or another of the above methods was dried at a temperature of 90-120 ° C until the solvent was almost completely removed (mainly the case when the template was removed by extraction with alcohol), then it was ground in a dispersant and weighed.

A portion of air-dry crushed mesoporous titanium dioxide was placed in a glass beaker and an aqueous solution of nickel salt was added to it (for this purpose, nickel chloride, nickel bromide or nickel sulfate, which were highly soluble in water, were mainly used). The volume of the added solution was chosen in such a way as to ensure complete wetting of the crushed titanium dioxide and the possibility of efficient mixing of the mixture. In this case, the concentration of the solution of nickel salt was chosen such that 0.5 to 2 wt.% Salt in terms of nickel accounted for a portion of titanium dioxide (a decrease in the concentration of nickel salt below the lower limit leads to a sharp decrease in the photocatalytic activity of the finished product, and an increase in the salt concentration it does not make sense above the upper limit, since this does not contribute to an increase in the photocatalytic activity of the finished product). Stirring the mixture, titanium dioxide at room temperature was treated with the solution until it completely adsorbed nickel ions from the solution. The time of such processing for each specific sample of ground titanium dioxide was determined experimentally. The completeness of adsorption of nickel ions by mesopores of titanium dioxide was determined by a known method (see Krengold S.U. Catalimetry in the analysis of reagents and substances of high purity. - M .: Chemistry, 1983. - P.97) using the highly sensitive catalytic reaction of tiron oxidation with hydrogen peroxide , which in the presence of nickel ions is accompanied by the formation of colored products that absorb light in the region of 340 nm. After the analysis of the solution indicated the absence of nickel ions in it, titanium dioxide adsorbing them was separated by filtration from the liquid phase, washed with distilled water on the filter, and then placed in a glass beaker. An aqueous solution of alkali metal borohydride was added to the glass (stoichiometric amounts of potassium borohydride, sodium borohydride, or lithium borohydride were mainly used) and, while mixing the mixture, titanium dioxide was treated with it until nickel ions were almost completely reduced in its mesopores to metallic nickel. The reduction rate of nickel ions by this reducing agent is practically independent of temperature. Therefore, based on convenience, the reduction process was carried out at room temperature. The time of such processing for each specific sample of ground titanium dioxide adsorbing nickel ions was determined experimentally. We note the fact that even in the case when, as a result of the treatment of titanium dioxide with an alkali metal borohydride solution, the nickel reduction process in the mesopores of the sorbent was not completely completed, this did not affect the characteristics of the final product as a catalyst for the photochemical reactions of molecular hydrogen evolution, because . the first portions of hydrogen released (strong reducing agent) completely completed the recovery process.

Titanium dioxide containing metallic nickel in the mesopores was separated by filtration from the solution, washed on the filter with distilled water until a neutral reaction was reached, then washed with ethanol. The obtained composite nickel-semiconductor mesoporous material based on titanium dioxide was placed in a vacuum desiccator, where it was dried until a constant mass was achieved.

The proportion of metallic nickel in the final product (composite nickel-semiconductor mesoporous material based on titanium dioxide) was determined as follows. A portion of air-dry material was treated with a certain amount of hydrochloric acid. As a result of a chemical reaction, nickel chloride was obtained. Nickel ions were preliminarily extracted with dimethylglyoxime, after which their concentration in solution was determined by a known method (see ibid., P. 98). Knowing the total volume of the solution and the concentration of nickel ions in it, we calculated the total number of nickel ions in the solution, and, consequently, in the final product. Mesoporous titanium dioxide, from which nickel was extracted, was washed with distilled water, then dried in a vacuum desiccator until it reached a constant mass. The obtained mass value of nickel was correlated with the mass value of dry mesoporous titanium dioxide.

The specific surface of the obtained composite nickel-semiconductor mesoporous material based on titanium dioxide was calculated by the BET method (Brunauer-Emmett-Teller) from methanol adsorption isotherms using a well-known method (see, for example, Greg S., Sing K. Adsorption, specific surface, porosity. - M.: Mir, 1970. - P.73; or Brunauer S. Adsorption of gases and vapors. - M .: Inostr. lit., 1948, T. 1. - P.784). Adsorption and desorption isotherms of methyl alcohol were recorded at a temperature of 20 ° С by the adsorption gravimetric method using a Mac Ben-Bakr vacuum quartz balance with a sensitivity of 0.25-0.35 mm / mg (see, for example, M.M.Dubinin Physicochemical foundations of sorption technology. - 2nd ed., Rev. And add. - L .: ONTI, 1935. - 346 p .; or Experimental methods in adsorption and molecular chromatography // edited by A.V. Kiseleva 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 material 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 In this case, the sample of mesoporous material during this entire time was additionally thermostated at a temperature of about 100 ° C. 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. Based on the difference between the final and initial masses of the sample, taking into account the molecular weight of methanol, the amount of methanol (in mmol) adsorbed by the sample of mesoporous material upon reaching equilibrium was calculated and the adsorption value a (mmol / g) of methanol per gram of the sample was determined. Using the obtained value of a, the value of the methanol monolayer capacity am was determined using the BET equation (satisfactorily describing the initial portion of the adsorption isotherm of methanol vapor adsorption). As a result, the specific surface S _beats. (in m ² / g) of a sample of a mesoporous material based on titanium dioxide was calculated by the formula:

S _beats = a _m · N _A · Ú,

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 Avogadro number, mmol ^-1 , Ú is the size of the landing site of the methanol molecule, equal to 0.25 · 10 ^-18 m ² according to generally accepted ideas (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 the mesoporous material based on 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 a mesoporous material based on titanium dioxide, m ² / g, V _s = a · V _o is the maximum sorption pore volume, 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 saturated methanol vapor, and a is the adsorption limit (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 a mesoporous material based on titanium dioxide for the content of the anatase crystalline phase in them was performed on a DRON-3M diffractometer using copper, nickel-filtered, radiation at a voltage of 30 kV and a current strength of 20 mA, the slit when shooting in the small-angle 1.0- 1.0-0.5, in the middle and far corners - 2.0-2.0-1.0 (see, for example, L.I. Mirkin. Handbook of X-ray structural analysis of polycrystals. - M: State Publishing House of Physics and Physics and Mathematics, 1961. - 863 p .; or V.I. Mikheev. Radiometric determinant of minerals .-- .: Gosgeoltekhizdat, 1957. - 868 c).. The anatase content in the mesoporous material based on titanium dioxide was determined by the relative intensity of characteristic reflexes at 26 = 25.4 ° in comparison with a sample of dispersed material of the Degussa P 25 brand from Degussa, the anatase content of which is known.

The photocatalytic activity of the obtained samples of a mesoporous material based on 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 // Theoret. And Experimental Chemistry. - 1984.- Vol. 20, No. 2.- P.169-177). For this, a suspension consisting of 0.05 g of mesoporous material based on titanium dioxide and 10 ml of ethyl alcohol containing 2 mol / L of water was placed in a glass reactor. With constant stirring of the suspension at a temperature of 40 ° C, it was irradiated with the light of a high-pressure mercury lamp of the DRSh-1000 type, emitting quanta with a wavelength of about 360 nm using a UFS-2 glass filter. 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 _H2 ,

where n _{Fe (II)} is the number of iron (II) ions formed upon irradiation of a ferrioxalate solution, Ф _H2 , 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide:

Ф _Н2 = 2m _{Н2 / I} ,

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

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 a mesoporous material based on 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 is n-butanol containing water in an amount of 7 wt.%. 170 ml of this aqueous-alcoholic solvent was 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 500 ° C for 5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.22% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.13% aqueous sodium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in an amount of 38 wt.%, Nickel in an amount of 2.0 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0,091.

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 a mesoporous material based on 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 is 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 500 ° C for 5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.055% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.033% aqueous sodium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained an anatase crystalline phase in an amount of 55 wt.%, Nickel in an amount of 0.5 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0,092.

Example 4

An oxamacrocyclic compound dibenzo-30-corona-10 of the general formula C ₂₈ H ₄₀ O _{10 was} used as an organic template for the synthesis of a mesoporous material based on titanium dioxide, titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti, in as a water-alcohol solvent is n-butanol containing water in an amount of 5 wt.%. 180 ml of this aqueous-alcoholic 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 500 ° C for 5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.16% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.098% aqueous sodium borohydride solution was added to the beaker and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in an amount of 55 wt.%, Nickel in an amount of 1.5 wt.%, Had a porous structure with an average pore diameter of D _cp. = 9.3 nm and specific surface area S _beats. = 70 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.114.

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 a mesoporous material based on titanium dioxide, and titanium tetrabutoxide of the general formula (C ₄ H ₉ O) was used as a precursor ₄ Ti, as a water-alcohol solvent - n-butanol containing water in an amount of 7 wt.%. 167 ml of this aqueous-alcoholic solvent was poured into one glass beaker. At room temperature, 0.098 g of the template was dissolved in it. 45 ml of the same solvent was poured into another glass beaker. 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 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 500 ° C for 4.5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.079% aqueous nickel sulfate solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 3 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.055% aqueous potassium borohydride solution was added to the beaker and, while stirring the mixture, titanium dioxide was treated with it for 3.5 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

The mesoporous material based on titanium dioxide thus obtained contained an anatase crystalline phase in an amount of 47 wt.%, Nickel in an amount of 0.6 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.090.

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 a mesoporous material based on titanium dioxide, and titanium tetrapropoxide of the general formula (C ₃ H ₇ O) ₄ Ti was used as a precursor , as a water-alcohol solvent - n-propanol containing water in an amount of 5 wt.%. 141 ml of this aqueous-alcoholic solvent was poured into one glass beaker. 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 during this synthesis step 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 the relative humidity was 81% with 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.167% aqueous nickel bromide solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.033% aqueous lithium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

The titanium dioxide-based mesoporous material thus obtained contained an anatase crystalline phase in an amount of 42 wt.%, Nickel in an amount of 0.9 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0,092.

Example 7

A complex of the oxamacrocyclic tetramethyl-12-corona-4 compound 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 a mesoporous material based on titanium dioxide, and tetrabutoxide was used as a precursor titanium 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 aqueous-alcoholic solvent was poured into one glass beaker. 0.426 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 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 350 ° C for 7.5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.15% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.128% aqueous potassium borohydride solution was added to the beaker and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in an amount of 50 wt.%, Nickel in an amount of 1.4 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.106.

Example 8

A complex of the oxamacrocyclic compound tetramethyl-12-corona-4 with a 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 a mesoporous material based on titanium dioxide, and tetrabutoxide was used as a precursor titanium of the general formula (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 where the temperature 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at 450 ° C for 4.5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.18% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.112% aqueous sodium borohydride solution was added to the beaker and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

The mesoporous material based on titanium dioxide thus obtained contained an anatase crystalline phase in an amount of 56 wt.%, Nickel in an amount of 1.7 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.108.

Example 9

A complex of the oxamacrocyclic compound tetramethyl-12-corona-4 with a 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 a mesoporous material based on titanium dioxide, and tetrabutoxide was used as a precursor titanium of the general formula (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 where the temperature 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder 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. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.371% aqueous nickel bromide solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 3 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.183% aqueous potassium borohydride solution was added to the beaker and, while stirring the mixture, titanium dioxide was treated with it for 3.5 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in an amount of 32 wt.%, Nickel in an amount of 2.0 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.090.

Example 10

A complex of the oxamacrocyclic compound tetramethyl-12-corona-4 with a 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 a mesoporous material based on titanium dioxide, and tetrabutoxide was used as a precursor titanium of the general formula (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 where the temperature 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, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 450 ° C for 5.5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.090% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.054% aqueous sodium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

The mesoporous material based on titanium dioxide thus obtained contained an anatase crystalline phase in an amount of 53 wt.%, Nickel in an amount of 0.8 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.103.

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 · 3H ₂ O was used as an organic template for the synthesis of a mesoporous material based on titanium dioxide, and tetrabutoxide was used as a precursor titanium of the general formula (C ₄ H ₉ O) ₄ Ti; as a water-alcohol solvent, n-butanol containing 6.5 wt.% water. 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 during this synthesis step 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 500 ° C for 5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.18% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.062% aqueous lithium borohydride solution was added to the beaker and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in an amount of 64 wt.%, Nickel in an amount of 1.7 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.114.

Example 12

A complex of the oxamacrocyclic compound tetramethyl-12-corona-4 with a rubidium ion of the general formula [Rb (C ₁₂ H ₂₄ O ₄ )] Br ₃ H ₂ O was used as an organic template for the synthesis of a mesoporous material based on titanium dioxide, and tetrapropoxide was used as a precursor titanium of the general formula (C ₃ H ₇ O) ₄ Ti, as a water-alcohol solvent, n-propanol containing water in an amount of 5.5 wt.%. 145 ml of this aqueous-alcoholic solvent were 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 500 ° C for 4.5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.144% aqueous nickel sulfate solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 3 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.101% aqueous potassium borohydride solution was added to the beaker and, while stirring the mixture, titanium dioxide was treated with it for 3.5 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

The mesoporous material based on titanium dioxide thus obtained contained an anatase crystalline phase in an amount of 61 wt.%, Nickel in an amount of 1.1 wt.%, Had a porous structure with an average pore diameter of D _cp. = 12.1 nm and specific surface S _beats. = 110 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.109.

Example 13

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, we used a complex of the oxamacrocyclic compound tetramethyl-12-corona-4 with a cesium ion of the general formula [Cs (C ₁₂ H ₂₄ O ₄ )] NO ₃ · ₃ H ₂ O, as a precursor titanium tetrapropoxide of the general formula (C ₃ H ₇ O) ₄ Ti, as a water-alcohol solvent, n-propanol containing water in an amount of 4.5 wt.%. 136 ml of this aqueous-alcoholic solvent was poured into one 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 550 ° C for 5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.37% aqueous nickel bromide solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.183% aqueous potassium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

The mesoporous titanium dioxide-based mesoporous material contained anatase crystalline phase in an amount of 45 wt.%, Nickel in an amount of 2.0 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0,092.

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 a mesoporous material based on titanium dioxide, and as a precursor, titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti; as a water-alcohol solvent, n-butanol containing 6.5 wt.% water. 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 at this synthesis stage was maintained at about 14 ° C. After ash formation, the stirring of the mixture was stopped. A beaker 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% with 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. The formed structure was separated by filtration from the mother liquor, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 450 ° C for 5.5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.19% aqueous solution of nickel chloride were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.165% aqueous potassium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in an amount of 55 wt.%, Nickel in an amount of 1.8 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.110.

Example 15

A complex of the oxamacrocyclic compound tetramethyl-12-corona-4 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 a mesoporous material based on titanium dioxide, and 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.%. 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 500 ° C for 4.5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.22% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.13% aqueous sodium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in an amount of 52 wt.%, Nickel in an amount of 2.0 wt.%, Had a porous structure with an average pore diameter of D _cp. = 9.3 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.112.

Example 16

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, we used a complex of the oxamacrocyclic compound tetramethyl-12-corona-4 with a strontium ion of the general formula [Sr (C ₁₂ H ₂₄ O ₄ )] 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 7 wt.% water. 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 500 ° C for 4.5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.16% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.138% aqueous potassium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

The mesoporous material based on titanium dioxide thus obtained contained an anatase crystalline phase in an amount of 52 wt.%, Nickel in an amount of 1.5 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.103.

Example 17

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, we used 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, 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. 174 ml of this aqueous-alcoholic solvent was poured into one glass beaker. 0.338 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 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 glass with the mixture was placed in a chamber in which the temperature was maintained at about 35 ° C with a thermostat, and the relative humidity was 62% using 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, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.22% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.183% aqueous potassium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in an amount of 35 wt.%, Nickel in an amount of 2.0 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0,092.

Example 18

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, a complex of the oxamacrocyclic compound tetramethyl-12-corona-4 with a lanthanum ion of the general formula [La (C ₁₂ H ₂₄ O ₄ )] Cl 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 6 wt.% water. 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 500 ° C for 5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.30% aqueous nickel bromide solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 3 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.147% aqueous potassium borohydride solution was added to the glass and, while mixing the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in an amount of 51 wt.%, Nickel in an amount of 1.6 wt.%, Had a porous structure with an average pore diameter of D _cp. = 12.8 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.104.

Example 19

As an organic template for the synthesis of a mesoporous material based on 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 · ₃ H 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.%. 163 ml of this aqueous-alcoholic solvent was 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, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 500 ° C for 4.5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.22% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.183% aqueous potassium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

The mesoporous material based on titanium dioxide thus obtained contained an anatase crystalline phase in an amount of 61 wt.%, Nickel in an amount of 2.0 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.113.

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, as a precursor, was used as an organic template for the synthesis of a mesoporous material based on titanium dioxide - titanium tetrapropoxide of the general formula (C ₃ H ₇ 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 350 ° C for 6.5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.20% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.070% aqueous lithium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in an amount of 45 wt.%, Nickel in an amount of 1.9 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.093.

Example 21

A complex of the oxamacrocyclic compound dibenzo-18-corona-6 with a sodium ion of the general formula [Ma (C ₂₀ H ₂₄ O ₆ )] Cl · 3H ₂ O was used as an organic template for the synthesis of a mesoporous material based on titanium dioxide, tetrabutoxide was used as a precursor titanium 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 a 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 500 ° C for 5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.22% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.183% aqueous potassium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

The mesoporous titanium dioxide-based mesoporous material contained an anatase crystalline phase in an amount of 90 wt.%, Nickel in an amount of 2.0 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided the maximum possible quantum yield of the reaction Ф _H2 = 0.130.

Example 22

A complex of oxamacrocyclic compound dibenzo-18-corona-6 with a 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 a mesoporous material based on titanium dioxide, and titanium tetrapropoxide was used as a precursor of the general formula (C ₃ H ₇ O) ₄ Ti, methanol containing water in an amount of 6.5% by weight is used 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 during this synthesis step 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 450 ° C for 5.5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.17% aqueous nickel sulfate solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 3 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.048% aqueous lithium borohydride solution was added to the beaker and, while stirring the mixture, titanium dioxide was treated with it for 3.5 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in the amount of 71 wt.%, Nickel in the amount of 1.3 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.111.

Example 23

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, we used a complex of the oxamacrocyclic compound dibenzo-18-corona-6 with a rubidium ion of the general formula [Rb (С ₂₀ Н ₂₄ O ₆ )] Br · 3Н ₂ O, tetrabutoxide as a precursor titanium of the general formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent, n-butanol containing 6 wt.% water. 180 ml of this water-alcohol 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 500 ° C for 5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.09% aqueous solution of nickel chloride were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.073% aqueous potassium borohydride solution was added to the glass and, while mixing the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in an amount of 75 wt.%, Nickel in an amount of 0.8 wt.%, Had a porous structure with an average pore diameter of D _cp. = 12.0 nm and specific surface area S _beats. = 121 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.112.

Example 24

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, 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 a precursor - titanium tetraethoxide of the general formula (C ₂ H ₅ O) ₄ Ti, ethanol containing water in an amount of 5 wt.% as a water-alcohol solvent. 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 550 ° C for 5 hours until the template was completely removed from it. The result was 7.9 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 158 ml of a 0.17% aqueous solution of nickel chloride were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 158 ml of a 0.147% aqueous potassium borohydride solution was added to the glass and, while mixing the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

The titanium dioxide-based mesoporous material thus obtained contained an anatase crystalline phase in an amount of 72 wt.%, Nickel in an amount of 1.6 wt.%, Had a porous structure with an average pore diameter of D _cp. = 9.2 nm and specific surface area S _beats. = 90 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.123.

Example 25

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, a complex of oxamacrocyclic compound dibenzo-18-corona-6 with a magnesium ion of the general formula [Mg (C ₂₀ H ₂₄ O ₆ )] SO ₄ · 4H 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 6.5 wt.% water. 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.20% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.017% aqueous potassium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

The mesoporous material based on titanium dioxide thus obtained contained an anatase crystalline phase in an amount of 77 wt.%, Nickel in an amount of 1.9 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.122.

Example 26

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, 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 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

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 throughout this synthesis step was maintained at about 30 ° C. After ash formation, the stirring of the mixture was stopped. The beaker with the mixture was placed in a chamber, the temperature of which was maintained at about 30 ° 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 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 500 ° C for 4.5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.14% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.12% aqueous potassium borohydride solution was added to the glass and, while mixing the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in an amount of 58 wt.%, Nickel in an amount of 1.3 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.111.

Example 27

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, we used a complex of the 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, 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. 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 400 ° C for 5.5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.07% aqueous solution of nickel chloride were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.055% aqueous potassium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained an anatase crystalline phase in an amount of 62 wt.%, Nickel in an amount of 0.6 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.107.

Example 28

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, we used 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, 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.%. 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 at which the temperature was maintained at about 30 ° C with a thermostat, and a relative humidity of 75% with a saturated sodium chloride solution. The mixture was contacted with water vapor at this temperature for 17 days until the mixture was finally formed from the mixture 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.18% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.156% aqueous potassium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in an amount of 73 wt.%, Nickel in an amount of 1.7 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.120.

Example 29

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, we used a complex of the oxamacrocyclic compound dibenzo-18-corona-6 with a lanthanum ion of the general formula [La (С ₂₀ Н ₂₄ O ₆ )] Cl ₃ · 3Н 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. 175 ml of this aqueous-alcoholic solvent was poured into one glass beaker. 4.703 g of a 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 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 470 ° C for 5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.20% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.17% aqueous potassium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

The titanium dioxide-based mesoporous material thus obtained contained an anatase crystalline phase in an amount of 81 wt.%, Nickel in an amount of 1.9 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.125.

Example 30

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, we used 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, as a precursor titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent, n-butanol containing 6 wt.% water. 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 500 ° C for 4.5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.07% aqueous solution of nickel chloride were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.055% aqueous potassium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in an amount of 70 wt.%, Nickel in an amount of 0.6 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.115.

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 a mesoporous material based on titanium dioxide, tetrabutoxide was used as a precursor titanium of the general formula (C ₄ H ₉ O) ₄ Ti; as a water-alcohol solvent, n-butanol containing 7 wt.% water. 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 350 ° C for 5.5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.22% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.183% aqueous potassium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in an amount of 40 wt.%, Nickel in an amount of 2.0 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0,092.

Example 32

A complex of oxamacrocyclic compound dibenzo-30-corona-10 with potassium ion of the general formula [K (C ₂₈ H ₄₀ O ₁₀ )] J · 2H ₂ O was used as an organic template for the synthesis of a mesoporous material based on titanium dioxide, and tetrabutoxide was used as a precursor titanium of the general formula (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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 500 ° C for 5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.22% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.183% aqueous potassium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in an amount of 52 wt.%, Nickel in an amount of 2.0 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.107.

Example 33

A complex of oxamacrocyclic compound dibenzo-30-corona-10 with sodium ion of the general formula [Na (C ₂₈ H ₄₀ O ₁₀ )] Cl · 2H ₂ O was used as an organic template for the synthesis of a mesoporous material based on titanium dioxide, tetrabutoxide was used as a precursor titanium of the general formula (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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 400 ° C for 6 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.19% aqueous solution of nickel chloride were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.165% aqueous potassium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in an amount of 70 wt.%, Nickel in an amount of 1.8 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.124.

Example 34

A complex of 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 a mesoporous material based on titanium dioxide, tetrabutoxide as a precursor titanium of the general formula (C ₄ H ₉ O) ₄ Ti; as a water-alcohol solvent, n-butanol containing 6 wt.% water. 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 during this synthesis step 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 350 ° C for 6.5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.10% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.082% aqueous potassium borohydride solution was added to the beaker and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

The mesoporous material based on titanium dioxide thus obtained contained an anatase crystalline phase in an amount of 66 wt.%, Nickel in an amount of 0.9 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.116.

Example 35

A complex of the oxamacrocyclic compound dibenzo-24-corona-8 with a cesium ion of the general formula [Cs (С ₂₄ Н ₃₂ O ₈ )] NO ₃ · 4Н ₂ O was used as an organic template for the synthesis of a mesoporous material based on titanium dioxide, as a precursor - titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti; as a water-alcohol solvent, n-hexyl alcohol containing 6.5 wt.% water. 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 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 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 500 ° C for 5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.18% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.156% aqueous potassium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

The mesoporous material based on titanium dioxide thus obtained contained an anatase crystalline phase in an amount of 72 wt.%, Nickel in an amount of 1.7 wt.%, Had a porous structure with an average pore diameter of D _cp. = 12.7 nm and specific surface area S _beats. = 90 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.125.

Example 36

A complex of the 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 a mesoporous material based on titanium dioxide, and 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.%. 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 500 ° C for 5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.16% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.138% aqueous potassium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained an anatase crystalline phase in an amount of 65 wt.%, Nickel in an amount of 1.5 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.115.

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 a mesoporous material based on titanium dioxide, 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. 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.08% aqueous solution of nickel chloride were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.064% aqueous potassium borohydride solution was added to the beaker and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

The mesoporous material based on titanium dioxide thus obtained contained an anatase crystalline phase in an amount of 52 wt.%, Nickel in an amount of 0.7 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.103.

Example 38

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, we used a complex of oxamacrocyclic compound dibenzo-24-corona-6 with a strontium ion of the general formula [Sr (С ₂₄ Н ₃₄ O ₈ )] Cl ₂ · 2Н ₂ O, as a precursor - titanium tetraethoxide of the general formula (C ₂ H ₅ O) ₄ Ti, ethanol containing water in an amount of 6 wt.% as a water-alcohol solvent. 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed from it. The result was 7.9 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 158 ml of a 0.22% aqueous solution of nickel chloride was added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 158 ml of a 0.183% aqueous solution of potassium borohydride was added to the glass and, while mixing the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in an amount of 50 wt.%, Nickel in an amount of 2.0 wt.%, Had a porous structure with an average pore diameter of D _cp. = 12.0 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.106.

Example 39

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, we used a complex of oxamacrocyclic compounds dibenzo-30-corona-10 with a barium ion of the general formula [Ba (C ₂₈ H ₄₀ O ₁₀ )] Cl ₂ · 3H ₂ O, as a precursor titanium tetrapropoxide of the general formula (C ₄ H ₉ O) ₄ Ti; as a water-alcohol solvent, n-heptyl alcohol containing 7 wt.% water. 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 500 ° C for 4.5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.17% aqueous solution of nickel chloride were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.147% aqueous potassium borohydride solution was added to the glass and, while mixing the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

The mesoporous material based on titanium dioxide thus obtained contained an anatase crystalline phase in an amount of 54 wt.%, Nickel in an amount of 1.6 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.102.

Example 40

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, we used a complex of the oxamacrocyclic compound dibenzo-24-corona-3 with a lanthanum ion of the general formula [La (С ₂₄ Н ₃₂ O ₈ )] Cl ₃ · 3Н ₂ О, as a precursor - titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti; as a water-alcohol solvent, n-butanol containing 6 wt.% water. 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 500 ° C for 4.5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.22% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.183% aqueous potassium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in an amount of 70 wt.%, Nickel in an amount of 2.0 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.123.

Example 41

A complex of 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 a mesoporous material based on 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. 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.13% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.11% aqueous potassium borohydride solution was added to the beaker and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained an anatase crystalline phase in an amount of 65 wt.%, Nickel in an amount of 1.2 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.111.

Example 42

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, a complex of oxamacrocyclic compound dibenzo-24-corona-6 with a cerium ion of the general formula [Ce (C ₂₄ H ₃₂ O ₈ )] Cl 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. 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 structure was separated from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.22% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.183% aqueous potassium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

The mesoporous material based on titanium dioxide thus obtained contained an anatase crystalline phase in an amount of 61 wt.%, Nickel in an amount of 2.0 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.113.

Example 43

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, we used a complex of oxamacrocyclic compound dibenzo-24-corona-8 with a cerium ion of the general formula [Ce (C ₂₄ H ₃₂ O ₈ )] Cl ₃ · ₃ H 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. 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

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 result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.22% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.183% aqueous potassium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

The mesoporous material based on titanium dioxide thus obtained contained an anatase crystalline phase in an amount of 36 wt.%, Nickel in an amount of 2.0 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0,091.

Example 44

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, a complex of 18-Coronaaz-2-oxa-4 oxazamacrocyclic compound with a lithium ion of the general formula [Li (C ₁₂ H ₂₆ O ₄ N ₂ )] Cr · 3H ₂ O, in titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti is used as a precursor; n-butanol containing water in an amount of 5.5 wt.% is used as a water-alcohol solvent. 184 ml of this aqueous-alcoholic 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 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 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.22% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.183% aqueous potassium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in an amount of 76 wt.%, Nickel in an amount of 2.0 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.122.

Example 45

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, we used a complex of the oxazamacrocyclic 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, in titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti is used as a precursor; n-butanol containing 5 wt% water is used as a water-alcohol solvent. 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.22% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.183% aqueous potassium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in an amount of 74 wt.%, Nickel in an amount of 2.0 wt.%, Had a porous structure with an average pore diameter of D _cp. = 12.7 nm and specific surface area S _beats. = 105 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.123.

Example 46

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, 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, in titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti is used as a precursor; n-butanol containing 7 wt.% water is used as a water-alcohol solvent. 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.19% aqueous solution of nickel chloride were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.165% aqueous potassium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in an amount of 78 wt.%, Nickel in an amount of 1.8 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.125.

Example 47

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, we used a complex of oxazamacrocyclic compound 18-Coronaaz-2-oxa-4 with a rubidium ion of the general formula [Rb (C ₁₂ H ₂₆ O ₄ N ₂ )] Br · 3H ₂ O, in titanium tetraethoxide of the general formula (C ₂ H ₅ O) ₄ Ti is used as a precursor; ethanol containing 7 wt.% water is used as a water-alcohol solvent. 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed from it. The result was 7.9 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 158 ml of a 0.15% aqueous solution of nickel chloride was added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 158 ml of a 0.13% aqueous solution of potassium borohydride was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in an amount of 50 wt.%, Nickel in an amount of 1.4 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.103.

Example 48

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, a complex of 18-Coronaaz-2-oxa-4 oxazamacrocyclic compound with a cesium ion of the general formula [Cs (C ₁₂ H ₂₆ O ₄ N ₂ )] NO ₃ · 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. 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 during this synthesis step 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 500 ° C for 4.5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.22% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.183% aqueous potassium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in an amount of 53 wt.%, Nickel in an amount of 2.0 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.107.

Example 49

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, we used a complex of an oxaazamacrocyclic 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 500 ° C for 4.5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.22% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.183% aqueous potassium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

The mesoporous material based on titanium dioxide thus obtained contained an anatase crystalline phase in an amount of 61 wt.%, Nickel in an amount of 2.0 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.114.

Example 50

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, we used a complex of the 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, titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti is used as a precursor; n-butanol containing 4.5% by weight of water is used as a water-alcohol solvent. 170 ml of this aqueous-alcoholic solvent was 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 500 ° C for 4.5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.055% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.046% aqueous potassium borohydride solution was added to the glass and, while mixing the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in an amount of 64 wt.%, Nickel in an amount of 0.5 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.114.

Example 51

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, we used a complex of the 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, titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti is used as a precursor; n-butanol containing 4.5% by weight of water is used as a water-alcohol solvent. 170 ml of this aqueous-alcoholic solvent was 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 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

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 result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.22% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.183% aqueous potassium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

The titanium dioxide-based mesoporous material thus obtained contained an anatase crystalline phase in an amount of 34 wt.%, Nickel in an amount of 2.0 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.090.

Example 52

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, we used a complex of the 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 aqueous-alcoholic solvent was 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, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 500 ° C for 5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.16% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.138% aqueous potassium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in an amount of 61 wt.%, Nickel in an amount of 1.5 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.113.

Example 53

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, a complex of 18-Coronaaz-2-oxa-4 oxazamacrocyclic compound with a calcium ion of the general formula [Ca (C ₁₂ H ₂₆ O ₄ N ₂ )] Cl ₂ · 3H ₂ O, titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti is used as a precursor; n-butanol containing 4.5% by weight of water is used as a water-alcohol solvent. 170 ml of this aqueous-alcoholic solvent was 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, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.20% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.17% aqueous potassium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

The mesoporous material based on titanium dioxide thus obtained contained an anatase crystalline phase in an amount of 60 wt.%, Nickel in an amount of 1.9 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.112.

Example 54

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, we used a complex of oxazamacrocyclic compound 18-Coronaaz-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, titanium tetraisopropoxide of the general formula (C ₄ H ₉ O) ₄ Ti is used as a precursor; n-propanol containing water in an amount of 6.5 wt.% is used as a water-alcohol solvent. 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 500 ° C for 4.5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.22% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.183% aqueous potassium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

The titanium dioxide-based mesoporous material thus obtained contained an anatase crystalline phase in an amount of 69 wt.%, Nickel in an amount of 2.0 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.122.

Example 55

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, we used a complex of 18-Coronaaz-2-oxa-4 oxazamacrocyclic compound 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.16% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.138% aqueous potassium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

The mesoporous material based on titanium dioxide thus obtained contained an anatase crystalline phase in an amount of 72 wt.%, Nickel in an amount of 1.5 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.121.

Example 56

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, we used a complex of the oxazamacrocyclic compound 18-Coronaaz-2-oxa-4 with the 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.17% aqueous solution of nickel chloride were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.147% aqueous potassium borohydride solution was added to the glass and, while mixing the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in an amount of 70 wt.%, Nickel in an amount of 1.6 wt.%, Had a porous structure with an average pore diameter of D _cp. = 12.8 nm and specific surface S _beats. = 97 m ² / g. As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, such a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.122.

Example 57

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, we used a complex of oxazamacrocyclic compound 18-Coronaaz-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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.22% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.183% aqueous potassium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

The mesoporous material based on titanium dioxide thus obtained contained an anatase crystalline phase in an amount of 67 wt.%, Nickel in an amount of 2.0 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.121.

Example 58

As an organic template for the synthesis of a mesoporous material based on 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.11% aqueous solution of nickel chloride were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.091% aqueous potassium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in an amount of 76 wt.%, Nickel in an amount of 1.0 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.113.

Example 59

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, a complex of the oxazazamacrocyclic compound dibenzo-18-coronaase-1-oxa-5 with a potassium ion of the general formula [K (C ₂₀ H ₂₆ 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 500 ° C for 4.5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.19% aqueous solution of nickel chloride were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.165% aqueous potassium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in an amount of 80 wt.%, Nickel in an amount of 1.8 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.123.

Example 60

As an organic template for the synthesis of a mesoporous material based on 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 ₂₆ 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 during this synthesis step 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 the relative humidity was 81% with 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.055% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.046% aqueous potassium borohydride solution was added to the glass and, while mixing the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in an amount of 78 wt.%, Nickel in an amount of 0.5 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.116.

Example 61

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, a complex of oxazamacrocyclic compound dibenzo-18-coronaase-1-oxa-5 with a 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 ₂ H ₅ O) ₄ Ti; as a water-alcohol solvent, ethanol containing 4 wt.% water. 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed from it. The result was 7.9 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 158 ml of a 0.22% aqueous solution of nickel chloride was added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 158 ml of a 0.183% aqueous solution of potassium borohydride was added to the glass and, while mixing the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in an amount of 52 wt.%, Nickel in an amount of 2.0 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.112.

Example 62

As an organic template for the synthesis of a mesoporous material based on 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 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.%. 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 400 ° C for 6 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.15% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.13% aqueous solution of potassium borohydride was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained an anatase crystalline phase in an amount of 58 wt.%, Nickel in an amount of 1.4 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.111.

Example 63

As an organic template for the synthesis of a mesoporous material based on 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 a precursor, 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 that, the structure together with the mother liquor was removed from the autoclave. The structure was separated from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 500 ° C for 5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.19% aqueous solution of nickel chloride were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.12% aqueous sodium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

The mesoporous material based on titanium dioxide thus obtained contained an anatase crystalline phase in an amount of 68 wt.%, Nickel in an amount of 1.8 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.120.

Example 64

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, we used a complex of the oxazazamacrocyclic 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 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. 170 ml of this aqueous-alcoholic 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.157% aqueous nickel sulfate solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.044% aqueous lithium borohydride solution was added to the beaker and, while mixing the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

The mesoporous material based on titanium dioxide thus obtained contained an anatase crystalline phase in an amount of 66 wt.%, Nickel in an amount of 1.2 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.112.

Example 65

As an organic template for the synthesis of a mesoporous material based on 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 a precursor, titanium tetrapropoxide of the general formula (C ₃ H ₇ O) ₄ Ti, as a water-alcohol solvent, n-propanol containing water in an amount of 6.5 wt.%. 143 ml of this aqueous-alcoholic solvent was poured into one glass beaker. 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 400 ° C for 5.5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.278% aqueous nickel bromide solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 3 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.138% aqueous potassium borohydride solution was added to the beaker and, while stirring the mixture, titanium dioxide was treated with it for 3.5 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

The mesoporous material based on titanium dioxide thus obtained contained an anatase crystalline phase in an amount of 63 wt.%, Nickel in an amount of 1.5 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.120.

Example 66

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, we used a complex of 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 a precursor, titanium tetrabutoxide of the general formula (C ₄ H ₉ O) ₄ Ti, as a water-alcohol solvent, 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.22% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.13% aqueous sodium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in an amount of 71 wt.%, Nickel in an amount of 2.0 wt.%, Had a porous structure with an average pore diameter of D _cp. = 12.1 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.122.

Example 67

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, we used a complex of the oxazamacrocyclic compound dibenzo-18-coronaase-1-oxa-5 with a lanthanum ion of the general formula [La (C ₂₀ H ₂₅ O ₅ N)] 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 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 500 ° C for 4.5 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.20% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.126% aqueous sodium borohydride solution was added to the beaker and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

Thus obtained mesoporous material based on titanium dioxide contained anatase crystalline phase in an amount of 76 wt.%, Nickel in an amount of 1.9 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.121.

Example 68

As an organic template for the synthesis of a mesoporous material based on titanium dioxide, we used a complex of the 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 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.%. 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 from the mother liquor by filtration, dried until the solvent was almost completely removed from it, then crushed in a dispersant.

To obtain mesoporous titanium dioxide, dry structure powder was poured into a crucible. The crucible was placed in a muffle furnace, where the structure was calcined at a temperature of 600 ° C for 4 hours until the template was completely removed from it. The result was 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide was ground in a dispersant, then transferred to a glass beaker. 150 ml of a 0.22% aqueous nickel chloride solution were added thereto. While mixing the mixture, titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide adsorbed nickel ions from the solution was separated by filtration from the liquid phase, washed on the filter with distilled water, then placed in a glass beaker. 150 ml of a 0.13% aqueous sodium borohydride solution was added to the glass and, while stirring the mixture, titanium dioxide was treated with it for 3 hours. The solid phase was separated by filtration from the suspension, washed on a filter with distilled water, then ethanol, and then dried in a vacuum desiccator until a constant mass was achieved.

The mesoporous material based on titanium dioxide thus obtained contained an anatase crystalline phase in an amount of 72 wt.%, Nickel in an amount of 2.0 wt.%, Had a porous structure with an average pore diameter of 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 a composite nickel-semiconductor mesoporous material based on titanium dioxide provided a quantum yield of the reaction Ф _H2 = 0.124.

The given examples do not exhaust all the possibilities of the practical embodiment of the inventive concept. Thus, in a more complex form of implementing the inventive concept, which does not contradict the main claims, at the stage of synthesis of a mesoporous material based on 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 the recommended lower limit, it is possible to maintain a different one from that at which the mixture is maintained at the previous stage of synthesis (from mixing creates reagents to zoloobrazovaniya). In addition, in the case when the ambient temperature and its humidity during the time from mixing the reagent solutions to the final formation of the spatial structure of the precursor / organic template from the reaction mixture change insignificantly, changes in these environmental parameters are predictable and correspond to the synthesis conditions, these synthesis steps a mesoporous material based on titanium dioxide can be carried out without using a thermostat and saturated solutions of the corresponding salts.

Industrial applicability

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

The mesoporous material obtained according to the procedure described in Example 21 and fixed as a thin layer on a glass plate was also tested as a sorbent-catalyst for the heterogeneous photochemical reaction of acetone oxidation in the gas phase. For comparison, we used a non-porous highly dispersed pyrogenic 100% anatase fixed in the form of a layer of the same thickness on another glass plate. The masses of the sample of mesoporous material and the sample of 100% anatase deposited on the plates were the same and amounted to 0.25 g. Photocatalytic oxidation of acetone vapor was carried out at room temperature with atmospheric oxygen. A plate with a layer of mesoporous material was placed in a closed glass reactor with a volume of 275 ml. A plate with a layer of pore-free 100% anatase was placed in another same reactor. The introduction of the same initial amount of acetone vapor (up to a concentration of 5 · 10 ^-3 mol / L) into the reactors, as well as sampling for the chromatographic determination of the content of acetone and its photocatalytic oxidation products, was carried out using a batcher through elastic rubber membranes hermetically integrated into reactor walls. Through the glass windows in the walls of the reactors, the sample plates were irradiated for 60 minutes with a DRSh-1000 type mercury lamp with light λ> 310 nm (light intensity - 2.7 · 10 ^-6 Einstein / min). The photocatalytic activity of the samples was evaluated by the degree of conversion (conversion) of acetone K,%, which was calculated by the formula

K = (C ₁ -C ₂ ) · 100 / C ₁ ,

where C ₁ is the initial concentration of acetone in each of the reactors (5 · 10 ^-3 mol / l); C ₂ is the concentration of acetone in each of the reactors at the end of the irradiation of the plates with the samples.

For a sample of mesoporous material obtained by the method described in example 21, the value of K = 43%. For a sample of nonporous 100% anatase, K = 17. Thus, the photocatalytic activity of the proposed mesoporous material is almost 2.5 times higher than the activity of a highly dispersed pyrogenic 100% anatase that does not have a porous structure. Moreover, as shown by the results of chromatographic analysis, during the photocatalytic oxidation of acetone with atmospheric oxygen in the presence of the inventive sorbent-catalyst, no reaction products other than carbon dioxide were detected.

Claims (7)

1. The catalyst for photochemical reactions, which is a mesoporous material based on titanium dioxide, characterized in that it contains a crystalline anatase phase in an amount of at least 30 wt.%, Nickel in an amount of from 0.5 to 2 wt.%, Has a porous structure with with an average pore diameter of 2 to 16 nm, a specific surface area of at least 70 m ² / g, and as a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures, it provides a quantum yield of the reaction from 0.09 to 0.13. 2. The catalyst for photochemical reactions according to claim 1, characterized in that it further comprises lanthanum in an amount of not more than 0.019 grams per gram of titanium dioxide contained in the material. 3. The method of producing a catalyst for photochemical reactions according to claim 1, comprising introducing a precursor of titanium tetraalkoxide and an organic template into an aqueous-organic solvent, holding the mixture of reagents until the spatial structure is finally formed from it through successive stages of sol formation, and then the gel, separating the obtained the 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 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 into the solvent or f-metals, consisting of lithium, potassium, sodium, rubidium, cesium, magnesium, calcium, strontium, barium, lanthanum and cerium, in an amount of from 0.001 to 0.2 moles per mole of precursor, until the formation of sol, the mixture of reagents mix, maintaining its temperature not higher than 35 ° C, until the final formation of the spatial structure of the reagents from the mixture, the mixture is kept at the same temperature in an open vessel under free access to a mixture of water vapor and after removing the template from the spatial structure, it is first treated with a solution of nickel salt, and then with an alkali metal borohydride solution to form metallic nickel. 4. The method according to claim 3, characterized in that the template is removed from the obtained reaction product by calcination at a temperature of from 300 to 600 ° C. 5. The method according to claim 3, characterized in that before removing the template, the reaction product is treated hydrothermally at a temperature of from 100 to 200 ° C and the template is removed from the reaction product by extraction with alcohol. 6. The method according to claim 4, characterized in that before removing the template, the reaction product is treated hydrothermally at a temperature of from 100 to 200 ° C. 7. The method according to claim 3, characterized in that the lanthanum salt is additionally introduced into the water-alcohol solvent, provided that the template does not contain lanthanum ion.