Catalyst for photo-chemical reactions on base of titanium dioxide and method of production of such catalyst

FIELD: composition and structure of composite metal semiconductor meso-porous materials; titanium-dioxide-based catalyst for photo-chemical reactions.

SUBSTANCE: proposed catalyst is meso-porous titanium-dioxide-based material containing crystalline phase of anatase in the amount no less than 30 mass-% and nickel in the amount no less than 2 mass-%; material has porous structure at average diameter of pores from 2 to 16 nm and specific surface no less than 70 m2/g; as catalyst of photo-chemical reaction of liberation of hydrogen from aqua-alcohol mixtures, it ensures quantum reaction yield from 0.09 to 0.13. Method of production of such catalyst includes introduction of precursor - titanium tetraalkoxyde and template of organic nature, holding reagent mixture till final molding of three-dimensional structure from it at successive stages of forming sol, then gel, separation of reaction product and treatment of this product till removal of template; process is carried out in aqua-alcohol solvent containing no more than 7 mass-% of water; at least one of ligands is introduced into solvent as template; ligand is selected from group of macro-cyclic compounds containing no less than four atoms of oxygen and/or from complexes of said macro-cyclic compounds with ions of metals selected from alkaline or alkaline-earth metals or F-metals containing lithium, potassium, sodium, rubidium, cesium, magnesium, calcium, strontium, barium, lanthanum and cerium; mixture is stirred before forming of sol maintaining its temperature not above 35°C till final molding of three-dimensional structure from reagent mixture; mixture is held in open reservoir at the same temperature at free access of water vapor; after removal of template from three-dimensional structure, mixture is first treated with nickel salt solution during period of time sufficient for withdrawal of nickel ions from solution by pores of structure, after which is it kept in hydrogen-containing medium during period of time sufficient for reduction of nickel ions in pores of structure to metallic nickel.

EFFECT: enhanced sorption and photo-catalytic parameters; reproducibility of catalyst properties.

7 cl, 68 ex

 

The technical field

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

Such composite metal-containing mesoporous materials without involving catalysts "dark" stages of reactions can be used:

as catalysts for photochemical reactions in chemical plants, in particular, to obtain molecular hydrogen as a vehicle fuel or as a source reagent for such processes as the synthesis of ammonia, methanol and the like;

as sorbents-photocatalysts for cleaning, for example, air and industrial effluents from harmful organic compounds by heterogeneous photocatalytic oxidation of the above-mentioned compounds to form a safe for human health products.

As used hereinafter, the terms applicable to the invention, means:

photocatalytic reaction is taking place under the action of light reaction, which involves compounds that undergo chemical transformations, and photocatalysts as substances that are not part of stoichiometric in the overall process;

the catalyst for photochemical reactions (photocatalyst) is a substance that absorbs the light, being indie is idealna or in combination with one of the reagents, resulting gains the ability to induce chemical transformations, transferring the energy of electronic excitation of the substrate or joining with him in the interim chemical interaction, and, in addition, regenerates its chemical composition and basic electronic state after each such cycle;

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

quantum yield is one of the main characteristics of photocatalytic reactions, indicating what proportion of the reagent molecules undergoing chemical transformation of one quantum of absorbed light photocatalyst;

templat - material serving strukturanalyse agent ("template"), where in the process the Sol-gel synthesis with a specific orientation in space fixed source reagents and which is formed by the structure of the dispersed porous material;

precursor - the original substance in the chemical reactions, for example hydrolysis, becomes a source material for forming the template during Sol-gel synthesis of porous skeleton dispersed material;

Sol is a colloidal system with liquid on spersonal environment, the particles of the dispersed phase (micelles) are freely engaged in Brownian motion and that the coagulation turns into gel',

gel - structured colloidal system with a liquid dispersion medium in which the particles of the dispersed phase are connected together in a loose three-dimensional grid containing in its cells dispersive environment;

the coordination compound, complex and compound complex composition, in which the Central cation (complexing agents) coordinated ligands through their donor atoms of oxygen and/or nitrogen, and the number of coordinated atoms depends on the nature of the Central cation and the nature of the ligand;

macrocyclic the connection in which the donor atoms of oxygen and/or nitrogen linked, carbon bridges of different lengths, also containing hydrogen atoms and/or different substituents and which form one or more closed loops;

examanation connection (crown ether) - macrocyclic compound containing only donor atoms of oxygen;

oxazaborolidine connection - macrocyclic compound containing, along with the donor atoms of the oxygen atoms of nitrogen;

hydrothermal processing - the processing of materials in the conditions of high temperature and pressure under which the water and water is astory capable of dissolving substances, practically insoluble in normal conditions, and in which the source of inorganic substances are transformed into crystalline product;

the calcination the calcination of the material at high temperatures.

The level of technology

Dispersed materials based on titanium dioxide as catalysts for photochemical reactions allocation of molecular hydrogen or, for example, as sorbents-catalysts heterogeneous photochemical oxidation processes of organic compounds should provide:

the highest quantum yields of the reactions of formation of products (i.e. must have the maximum possible coefficient of performance);

the possibility of pre-and preferably uniform concentration of organic compounds on its active surface for efficient decomposition.

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

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

These requirements still managed to perform only some partial combinations.

So, known dispersed material brand Degussa P25 company Degussa, which mainly consists of crystalline modifications of titanium dioxide - anatase (see, for example, a web page of the firm Degussa: www.degussa.com/cn/producte.html). Namely anatase, being, as is well known, semiconductor OR-type, capable of oxidation and reduction simultaneously (see, for example, Balzani Century, Scandola F., Infelta P. and other Energy resources through the prism of photochemistry and catalysis: TRANS. from English. Ed. Mgracella. - M.: Mir, 1986. - S.): when the absorption of photons, electrons excited in the conduction band and holes are generated in the valence band, respectively taking part in the reactions of reduction and oxidation of the molecules in contact with the semiconductor. This crystalline modification of titanium dioxide, having significantly fewer defects compared to its amorphous modification, on the one hand, facilitates the efficient movement of photogenerated charges in the bulk semiconductor, and on the other reduces the likelihood of leakage is highly undesirable reverse process of recombination of photogenerated charges. Therefore, a known catalyst material photochemical reactions and, in particular, such reactions as the release of molecular hydrogen from water-alcohol mixtures, characterized by high values of the quantum is ichudov the formation of hydrogen (about 0.4), provided additional use of the very expensive platinum or palladium catalyst the dark phase of these reactions, which is usually applied to the individual fine inert carrier such as silica gel, and the role which, as is well known (see, for example, Balzani Century, Scandola F., Infelta P. and other Energy resources through the prism of photochemistry and catalysis: TRANS. from English. Ed. Mgracella. - M.: Mir, 1986. - S)is the accumulation resulting from the reaction of atomic hydrogen and its conversion into molecular hydrogen.

However, the known dispersion grade material Degussa P25 has almost dense structure and is therefore very small specific surface area (about 50 m2/g of substance), formed of fine particles of material. Therefore, the utilization of this material for pre-concentrating on its active surface vapours of organic compounds with a view to their subsequent heterogeneous photochemical decomposition is very low. In addition, for the effective functioning of this material as a photocatalyst reaction of molecular hydrogen formation requires intensive mixing it with fine metal carrier catalyst, the dark reaction stage, as only a close contact of particles of semiconductor photocatalyst and grains carrier with the catalyst of the dark stage of decoupling footage aerovane in the semiconductor charges accumulation on metal photogenerated electrons, the discharge protonated water molecules on the metal surface, recombinatio formed of atoms of hydrogen and desorption of molecular hydrogen (see ibid.). Obviously, if you had to use in the mixing mode fine carrier metal catalyst for a significant part of the light radiation directed into the reactor, scatters and misses on the photocatalyst. It is also obvious that the result of intensive mixing of the reaction mixture is gradually abrasive wear as the photocatalyst particles and particles of a catalyst carrier dark stage reaction with loss, in particular, are very expensive precious metal.

A method of obtaining a crystalline modification of titanium dioxide - anatase, which is mainly material Degussa P25, a well-known (see, for example, Guidance on inorganic synthesis. Edited Gbauer. - M.: Mir, 1985. - V.4 - S-1462). It includes an introduction to tetraethoxide (ataxic, isopropoxide or piperonyl) titanium cooling (temperature about 5° (C) and vigorous stirring repeated (with respect to stoichiometric) amount of water to form a Muti hydrate oxide of titanium, stirring the mixture for several hours until complete hydrolysis of tetraethoxy is and titanium, filtering the obtained precipitate, washing it with water, vacuum dried at room temperature and subsequent heating at temperatures up to 400°to form a crystalline modification of titanium dioxide - anatase and grinding.

This known method is relatively simple and, in addition, provides almost 100%yield, having photocatalytic properties.

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

Also known mesoporous material based on titanium dioxide, having a much greater compared with the material Degussa P25 specific surface area (see, for example, application U.S. No. 679029 filed 12.06.96). Due to the mesoporous structure and therefore highly developed specific surface known material has a high absorption capacity. Therefore, it can be a good hub vapours of organic compounds subject to further decomposition.

However, the known material consists mainly of an amorphous phase of titanium dioxide and therefore ineffective as a catalyst for photochemical reactions allocation of molecular hydrogen and especially as a sorbent-catalyst heterogeneous photochemical oxidation processes'or is hanicheskih compounds in the gas phase.

The method of obtaining such a mesoporous material based on titanium dioxide template by Sol-gel synthesis includes (see ibid) introduction to aqueous organic solvent and precursor in the form of tetraethoxide titanium and a template in the form of organic compounds, mainly selected from among surfactants, exposure or processing of the obtained solution under certain conditions and modes to the formation of a mixture of precursor/templat first Zola, and then the gel and remove the template.

This method allows you to get arbconnection material based on titanium dioxide with an average pore diameter of about 3 nm and a specific surface area of up to 700 m2/year

However, this method does not allow to obtain mesoporous material based on titanium dioxide having 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 a method thereof, which are known from the article Synthesis of Hexagonally Packed Mesoporous TiO2by a Modified Sol-Gel Method. David M.Antonelli, Jackie Y.Ying // Angew.Chem.Int. Ed.Engl., 1995, V.34, No. 1, P.2014-2022 and article Synthesis, Characterization, and Photocatalytik Aktivity of Titania and Niobia Mesoporous Molekular Sieves. Viktor F.Stone, Jr. and Robert J.Davis // Chemistry of Materials, 1998, 10, No. 5, P.1468-1474. In the first of these articles described the texture of the material, is selected as a prototype, and Paladino described process is the prototype of receipt of such material, indicating conditions for each stage of the synthesis. The second (by other authors) studied the photocatalytic material properties of the prototype and an explanation of the nature of its photocatalytic activity.

Known mesoporous material based on titanium dioxide (see Synthesis of Hexagonally Packed Mesoporous TiO2by a Modified Sol-Gel Method. David M.Antonelli, Jackie Y.Ying // Angew.Chem.Int. 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 m2/, Therefore it is effective as a hub vapours of organic compounds.

However, this mesoporous material based on titanium dioxide is characterized by a rather low value of the quantum yield of formation of molecular hydrogen (less than 0.01), provided additional use in the mixing mode of the platinum or palladium catalyst the dark stages 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, 10, No. 5, P.1470, table 1), indicating that the prevalence of the photocatalytic material of low amorphous phase titanium dioxide (see ibid., s, figure 4). In addition, the decrease in photocatalytic activity of the known material contributes to the content in its pores fragment temple is TA - phosphorus (see ibid.). Therefore, this mesoporous material based on titanium dioxide for complex properties are not efficient enough and as a sorbent-photocatalyst.

The method of obtaining known mesoporous material based on titanium dioxide includes (see Synthesis of Hexagonally Packed Mesoporous TiO2by a Modified Sol-Gel Method. David M.Antonelli, Jackie Y.Ying // Angew.Chem.Int. Ed.Engl., 1995, V.34, No. 1, P.2017) dissolving in water a template - monododecanoate and regulator of pH potassium hydroxide, dissolved in an organic solvent - acetylacetone - precursor in the form of tetraethoxide (isopropoxide) titanium, mixing the resulting solutions, aging the mixture at a temperature of about 80°isolated from the external environment of the vessel to the final formation of spatial patterns, which, as is well known, includes an intermediate stage of education first, Zola, and then the gel (see, for example, Chemical encyclopedic dictionary / edited Elecronica. - Moscow: Soviet encyclopedia, 1983. - S), sludge separation, washing, drying and processing to remove from the template.

There is a method allows to obtain a mesoporous material based on titanium dioxide with a well-ordered pore structure and large surface (see Synthesis of Hexagonally Packed Mesoporous TiO2by a Modified Sol-Gel Method. David M.Antonelli, Jackie Y.Ying // Angew.Chem.Int. Ed.Engl., 1995, V.34, No. 1, P.2017).

However, this act is about not possible to obtain mesoporous material based on titanium dioxide with a high content of photocatalytic active crystalline phase - of anatase. In addition, the use in accordance with the known method of monododecanoate as templateloader reagent prevents the complete removal of fragments of the 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, 10, No. 5, P.1471).

The invention

In the group of inventions based on task by improving the composition and texture mesoporous material based on titanium dioxide to create a composite metal-semiconductor mesoporous material based on titanium dioxide with high sorption and photocatalytic performance and by the selection of reagents for the method of obtaining such mesoporous materials and synthesis conditions to ensure reproducibility of the complex properties of the sorbent-photocatalyst.

The problem is solved by the fact that mesoporous material based on titanium dioxide according to the invention contains a crystalline phase of anatase in the amount of not less than 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, specific surface area of not less than 70 m2/g / and as a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures provides the quantum yield of the reaction from 0.09 to 0.13.

Per the second additional difference lies in the fact, he further comprises lanthanum in an amount of not more 0,019 grams per gram of titanium dioxide contained in the material.

The problem is solved in a method of producing mesoporous material based on titanium dioxide, including the introduction of water-organic solvent precursor - tetraethoxide titanium and a template of organic nature, the extract of the mixture of reactants to the final formation of spatial patterns through successive stages of education Zola, and then gel, the separation of the obtained reaction product and its processing to delete a template, according to the invention the process is carried out in aqueous-alcoholic solvent containing not more than 7 wt.% water, as a template in a solvent is injected at least one ligand selected from the group of macrocyclic compounds, consisting of oxa - and oxazaborolidine compounds containing at least four oxygen atoms, and/or complexes of these macrocyclic 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, before the formation of Zola mixture of the reactants stirred, maintaining the temperature not above 35°With, before the final formation of MESI reagents spatial structure of the mixture is maintained at the same temperature in an open vessel under conditions of free access to the mixture of water vapor and after removal of the spatial structure of the template it first process the Nickel salt solution for a time sufficient to extract ions from a solution of Nickel pore structure, and then aged in a hydrogen-containing atmosphere for a time sufficient for recovery of the Nickel ions in the pore structure of the metal Nickel.

The first additional difference is that template removed from the obtained reaction product by calcining at a temperature of from 300°to 600°C. the Use of such modes of annealing promotes the almost complete removal of the reaction product template, deep directed crystallization of the material with primary education phase of anatase and, as a consequence, obtaining photocatalytic active material of the sorbent.

A second difference is that template removed from the reaction product by extraction with alcohol. This alternative to the previous, also enables you to almost completely remove organic template from the reaction product.

The third additional to the first and second difference is that before removing the template, the reaction product is treated hydrothermally at a temperature of from 100°to 200°C. a Combination of hydrothermal treatment of the product with the techniques of his getimplfileline can be almost fully complete idalis of tetraethoxide titanium, to form a photocatalytic active phase of anatase and save the parameters generated mesoporous structure after the almost complete removal of the organic template from the reaction product.

Fourth difference is that in aqueous-alcoholic solvent is further added salt of lanthanum. This can further increase thermal stability of the inorganic component of the spatial structure of titanium dioxide/organic template with its subsequent thermal treatment and eventually advanced to stabilize the mesoporous structure of the final product without changing its photocatalytic properties.

The best ways to embodiments of the inventions

Further, the essence of invention is illustrated generalized examples of the method of obtaining a mesoporous material based on titanium dioxide, methods of determining the parameters of the porous structure of the final product (composite metal-semiconductor mesoporous material based on titanium dioxide), a method of determining the phase composition of the final product and the methodology of evaluation of photocatalytic properties of the finished product on the example of its use as a catalyst for photochemical reactions allocation of molecular hydrogen from water-alcohol mixtures.

The essence of the group image is eteni explains specific examples of the method of obtaining a mesoporous material based on titanium dioxide, in which are defined by these methods (without repeated references to them) parameters of the porous structure, structure and photocatalytic properties of the obtained composite metal-semiconductor mesoporous material based on titanium dioxide.

Example 1. Generalized method of obtaining a mesoporous material based on titanium dioxide, generalized methods of determining the parameters of the porous structure, structure and photocatalytic properties of mesoporous material based on titanium dioxide.

As an organic template for the synthesis of mesoporous material based on titanium dioxide used at least one oxa or oxazaborolidine compounds containing at least four oxygen atoms (preferably no more than ten) and/or one of the complexes called macrocyclic compounds with alkaline ion (lithium, sodium, potassium, rubidium, cesium)or alkaline earth (magnesium, calcium, strontium, barium), or f-metals (lanthanum, cerium). Note that the organic template in the form of oxa - and oxazaborolidine compounds, and complexes of these compounds with the above metals, which contain less than four oxygen atoms, are not described in literature. The use of oxa - and oxazaborolidine compounds and their complexes with these metals, who will win ten or more oxygen atoms, it is not excluded, but, as evidenced by the results of our research, this increases the likelihood of an inhomogeneous structure of the mesoporous material and disrupt the stability of the parameters of its texture.

As a precursor of tetraethoxide titanium for the synthesis of mesoporous material based on titanium dioxide used tetraethoxy titanium, tetraisopropoxide titanium, tetraethoxy titanium, tetrapropoxide titanium or tetrabutoxide titanium.

As a water-alcohol solvent for the synthesis of mesoporous material based on titanium dioxide used methyl, ethyl, propyl, butyl, hexyl or amyl alcohols, the water content of which was not more than 7 wt.%. As shown by our experiments, it is possible to use other alcohols with a number of carbon atoms from two to nine, the water content of which does not exceed 7 wt.%. The use of such aqueous-alcoholic solvents with a high content of water is impractical because it leads to a significant acceleration of the process of hydrolysis of tetraethoxide titanium and, as a consequence, the violation of the homogeneity of the mesoporous structure of the final product.

Before the synthesis of the mesoporous material based on titanium dioxide was prepared portion of one of these substances, precursors and one randomly selected the data (named) substances-templates. On one mol of tetraethoxide titanium (precursor) was taken from 0.001 mole to 0.2 mole of the organic template. As we found out, the relative decrease in the number of template below the lower limit leads to the fact that the specific surface of the final product of the synthesis is obtained underdeveloped (less than 70 m2/g), which affects the sorption properties of the product. Relative increase in the number of the template above the upper limit is impractical, as it templat remains in excess, only partially taking part in the synthesis.

Glass poured one of the water-alcohol solvent in a quantity sufficient to dissolve the portion of the substance of the template at room temperature. In another glass beaker was filled with the same solvent in a quantity sufficient to dissolve the portion of the substance of the precursor at the same temperature. In some cases, when template used for the synthesis of mesoporous material based on titanium dioxide, was one of oxa - or oxazaborolidine compounds or complex of one of these macrocyclic compounds not containing lanthanum ion in aqueous-alcoholic solvent, in addition to the template was introduced salt of lanthanum in an amount of not more than 0,006 mol for one mol of tetraethoxide titanium (precursor). After th is increasing in the ground glass of a solution of a substance is a template or a mixture of substances is a template with a salt of lanthanum, and in the second glass - solution of the substance precursor into the contents of the first beaker with vigorous stirring was introduced dropwise a solution of the substance precursor. After all the cement substance precursor was introduced into the solution of the substance of the template, the resulting mixture was continued to stir for several hours prior to the formation of a mixture of Zola. As saloobrazovanie accompanied by a sharp increase in the viscosity of the mixture, the completion of this stage of the synthesis process is easily fixed, for example, by a sharp decrease in the rotation speed of electric mixer. The temperature of the mixture at this stage of the synthesis, starting from the mixing of the solutions and to samoobrazovaniem, supported not above 35°C. After saloobrazovanie, not stopping to maintain the temperature of the mixture not exceeding 35°With its stirring was stopped. The mixture was left in an open vessel under conditions of free access of water vapor from the environment (if the relative humidity of the environment was not less 60%) or put the vessel with the reaction mixture in the chamber where the relative humidity is not less than 60% specially created using saturated solutions of the corresponding salts by conventional methods (see, for example, chemist's Handbook / edited Bpiolar. M: Goskomizdat, 1963. Vol. 1, S). The contact of the mixture with water vapor provided within bore the channels at weeks prior to the final formation from the reaction mixture of the spatial structure of the titanium dioxide/templat. The criterion for completion of this phase synthesis served as clearly observed visually the effect of syneresis (see, for example, Chemical encyclopedia. M: Soviet encyclopedia, 1988, Vol. 1, S) - spontaneous final seal of the spatial structure of the titanium dioxide/templat and, as a consequence, the termination of eviction from her liquid phase.

For each individual for the synthesis of mesoporous material mixture specific reagents (precursor of the organic template and the water-alcohol solvent) the time of the final formation of the spatial structure of the composition of the titanium dioxide/organic template with different modes of synthesis was determined experimentally.

How did you manage to install, increasing the temperature of the reaction mixture in excess of the specified limit (35° (C) the stages of the synthesis of mesoporous material as saleabration and the formation of spatial patterns of the composition of the titanium dioxide/organic template, leads to deterioration of the texture characteristics of the final product and, above all, promotes the formation of a product with a small specific surface area. The lower set of experimental temperature limit at which to carry out these stages of the synthesis of the mesoporous material is 10°C. At lower temperatures there is a stable ten who ence to reduce the number of mesopores in the sample of the final product and, accordingly, increase in the amount of micropores.

Depending on the method chosen to remove the template (by calcination or extraction with alcohol) of the finally formed from a mixture of reagents spatial patterns and methods of obtaining the material necessary quantity of photocatalytic active anatase obtained spatial structure were subjected to various pre-processing.

When to remove a template from finally formirovanii spatial structure of titanium dioxide/templat and education material required number photocatalytic active anatase used the calcination, the structure of the pre-separated by filtration from the mother liquor, dried in the air to almost complete removal of the solvent, and then crushed in the dispersant. Dried powdered mixture was filled in 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 caliciviral at a temperature of from 300°to 600°C for 4-7 hours to remove the organic template. The criterion for complete removal from the structure of the template and obtain mesoporous titanium dioxide was the achievement of the contents of the crucible to constant weight after her loss in the process of the children is planirovanie, that was easily identified by consecutive weighing on an analytical balance of the crucible with its contents after they are cool. As shown by the results of x-ray phase analysis of the mesoporous titanium dioxide, the time allotted for getimplfileline patterns titanium dioxide/templat calcining according to the above method, it is quite enough for the formation of the titanium dioxide is not less than 30 wt.% photocatalytic active phase of anatase.

Note that almost all organic template listed in the claims, are removed from the spatial structure of titanium dioxide/templat already at the temperature of calcination 300°C. However, the duration of the calcination process structure at this temperature until complete removal of the template and complete the process of crystallization of titanium dioxide with primary education phase of anatase is about 7 hours. Therefore, to accelerate the process of full getimplfileline and education sufficient photocatalytic active phase of anatase calcination patterns titanium dioxide/templat osushestvljali at temperatures much higher, but not exceeding 600°C. this upper temperature limit of the value of specific surface area mesoporous material was significantly decreased, and obtain such material from odelin the second surface ≥ 70 m2/g was not possible. In addition, the calcination structure at temperatures above 600°contributed to the undesirable increase in the diameter of the mesopores in the material to the size of micropores.

In some cases, before finally calcining the formed spatial structure of titanium dioxide/templat she was subjected to hydrothermal treatment at a temperature of from 100°to 200°C. For this spatial structure together with the mother solution was placed in a sealed autoclave where the temperature is 100°s-200°and increased pressure arising at these temperatures, it was treated hydrothermally for about two days to complete hydrolysis of tetraethoxide titanium and the early formation of photocatalytic active phase of anatase. After that, the structure with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried her up to almost complete removal of the solvent, were crushed in the disperser, and then caliciviral with the aforementioned method. The resulting structure is almost completely removed templat started and completed during the hydrothermal treatment process education material required number photocatalytic active anatase.

Note that you can combine the process of calcination structure is ture titanium dioxide/templat with its preliminary hydrothermal processing is highly desirable, but not necessarily, as the calcination patterns even without prior training promotes the formation of a mesoporous material with the necessary number of photocatalytic active anatase.

In the case when template of finally formirovanii spatial structure of titanium dioxide/template was removed by extraction with alcohol, structure, not separating from the mother liquor, be sure to pre subjected to hydrothermal treatment in an autoclave for about four days at a temperature of from 100°to 200°C. Such regimes preliminary hydrothermal preparation contributed not only to the full completion of the hydrolysis of tetraethoxide, but also education in the mesoporous material required number photocatalytic active anatase.

After this preliminary hydrothermal processing structure with mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried her up to almost complete removal of the solvent, and then crushed in the dispersant. The obtained powder was placed in a glass beaker. Under vigorous stirring in a glass was added to pre-heated to the boiling point of the alcohol, mainly ethyl (one gram of powder patterns were taken about 300 g of alcohol), and extra what information was removed from formirovanii spatial structure of titanium dioxide/templat organic template. Avoiding strong cooling of the suspension, the filter was separated from her solid phase. Using the new batch of hot alcohol, separated by filtration solid phase twice more consistently treated by the same procedure. The result obtained mesoporous titanium dioxide, containing no organic template.

Mesoporous titanium dioxide obtained by varying the above, the method was dried at a temperature of 90-120°to practically complete removal of the solvent (mainly applies to the case when template was removed by extraction with alcohol, and then crushed in the dispersant and weighed.

A portion of air-dried powdered mesoporous titanium dioxide were placed in a glass beaker and added to it an aqueous solution of Nickel salts (predominantly been used well water-soluble Nickel chloride, Nickel bromide or Nickel sulfate). The volume of the added solution was chosen so as to ensure complete wetting of powdered titanium dioxide and efficient mixing. The concentration of Nickel salt solution was chosen such that the addition of titanium dioxide accounted for from 0.5 to 2 wt.% salt in terms of Nickel (decrease in the concentration of Nickel salts below the lower limit leads to a sharp decrease in fotokataliz the practical activity of the finished product, the increase of the salt concentration above the upper limit does not make sense, since it does not contribute to the increase of the photocatalytic activity of the finished product). Stirring the mixture of titanium dioxide at room temperature was treated with a solution as long as he did not fully adsorbing from solution of Nickel ions. The time of such processing for each specific sample of powdered titanium dioxide was determined experimentally. Completeness of adsorption of Nickel ions by mesopores of titanium dioxide was determined by known methods (see Reingold SO Katalimata in the analysis of chemicals and substances of high purity. - M, Chemistry, 1983. - S), using a highly sensitive catalytic oxidation reaction Tayrona 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 analysis of the solution indicated the absence of Nickel ions, filtering separated adsorbirovavshyei their titanium dioxide from the liquid phase, washed it on the filter with distilled water and dried to remove solvent.

To get in the mesopores of titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, Nickel metal, then it was kept in a hydrogen-containing atmosphere having reducing properties, in a period of time sufficient the CSOs to complete the recovery process.

The most rapid, does not require high energy costs and therefore, the most preferred was the next recovery process. Titanium dioxide containing mesopores of Nickel ions, were placed in a glass reactor. Based on 1 g of such titanium dioxide in the reactor was added 200 ml of ethanol containing 0.4 mol of water. The mixture in the reactor was intensively stirred until a homogeneous suspension, then the suspension was heated to a temperature of about 40°C. Through a glass filter UFS-2 (wavelength of about 360 nm), the suspension was irradiated with light of a mercury lamp high pressure type DRSH-1000. While titanium dioxide, absorbing quanta of light of a specified wavelength, as a photocatalyst contributed to the release of the water-alcohol solvent suspension is very strong regenerative properties of atomic hydrogen. Close contact of the reducing agent to Nickel ions contributed in turn fast enough to restore the last in the pores of the titanium dioxide to metallic Nickel. As the recovery of Nickel ions was increased and the amount of molecular hydrogen released from the suspension, so as Nickel metal acting as a catalyst the dark phase photochemical process, contributed to the accumulation resulting from the reactions is of atomic hydrogen and its conversion into molecular hydrogen. Controlling the rate of formation of molecular hydrogen gas chromatograph, was determined by the time the end of the recovery process on the output plot of the rate of formation of molecular hydrogen - time" on the saturation. The time of full recovery of Nickel ions in the pores of the titanium dioxide to metal according to this technique did not exceed 30-40 minutes.

Titanium dioxide containing mesopores of Nickel metal was separated by filtration from the suspension, washed on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

The proportion of Nickel metal in the final product (composite Nickel-semiconductor mesoporous material based on titanium dioxide) was determined as follows. A portion of air-dried material was treated with a certain amount of hydrochloric acid. As a result of chemical reactions received Nickel chloride. Nickel ions previously were extracted using dimethylglyoxime, then by well-known methods (see ibid., p.98) was determined by their concentration in solution. Knowing the total volume of solution and the concentration of Nickel ions, counted the total number of Nickel ions in solution, and hence in the final product. Mesoporous titanium dioxide, from which was extracted Nickel, washed dis is illirians water, then was dried in a vacuum desiccator until they reach constant weight. The obtained value of the mass of Nickel correlated with the value of the dry weight of 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) adsorption isotherms of methanol, using known methodology (see, for example, Greg S., Singh K. Adsorption, specific surface area, porosity. - M.: Mir, 1970. - S or S. Brunauer, the Adsorption of gases and vapors. - M.: Foreign Literature., 1948, Vol. 1. - S). Isotherms of adsorption and desorption of methyl alcohol was registrirovali at a temperature of 20°With the weight of the adsorption method using a vacuum installation with spring weights quartz poppy Ben-Bakr with a sensitivity of 0.25-0.35 mm/mg (see, for example, Mun. Physico-chemical fundamentals of sorption technology. - 2nd ed., revised and enlarged extra - L.: ONTI, 1935. - 346 C., or Experimental methods in adsorption and molecular chromatography /Ed. Avicelase and Wppreview. - M.: Moscow state University, 1973. - 448 C. or Nvilla. Fundamentals of adsorption technique. 2nd ed., revised and enlarged extra - M.: Chemistry, 1948, Vol. 1. - 592 C.). A portion of air-dried sample mesoporous material with a mass of about 0.1 g was placed in a glass Cup, which was hung on a quartz spring balance in the pipe vacuum the th installation. The cavity vacuum installation with the sample was evacuated for 3 hours, maintaining the residual pressure in the cavity that is equal to 10-3mm Hg While the sample mesoporous material throughout this time additionally thermostatically at a temperature of about 100°C. then, without changing the amount of the residual pressure in the cavity of the installation, the sample temperature was lowered to 20°C. using cathetometer with a multiplier of 0.01 mm was fixed initial value of the tension spring weights hung on the sample and the calibration table was determined by the initial mass of the sample, corresponding to this value of strain. Through the vacuum valve cavity installation hermetically connected with the vessel, partially filled with liquid methanol. He opened the faucet and methanol vapor above this liquid adsorption received in the cavity of the installation. The change in the value of the pressure in the cavity of the installation upon receipt in it of methanol vapor was detected by the mercury manometer. After the establishment of the system of equilibrium (reaching pressures in the cavity of the installation, equal to the saturated vapor pressure of methanol) pressure stabilized. Using cathetometer fixed finite tension spring weights hung on the sample and determine the final mass of the sample, with testwuide the value of stretching. On the difference between the final and initial weights of the sample taking into account the molecular weight of methanol was calculated amount of methanol (in mmol)adsorbed by the sample mesoporous material while achieving system balance and determined the amount of adsorption (mmol/g) of methanol in one gram of sample. Using the obtained value and the BET equation (satisfactorily describes the initial part of the isotherm of adsorption of vapors of methyl alcohol) was determined by the capacitance value of the monolayer of methanol andm. In the end, the specific surface Sbeats(m2/g) sample mesoporous material based on titanium dioxide was calculated by the formula

Sbeats=andm·NA·S,

where am- calculated by the BET equation (for the initial field of adsorption isotherms of methanol) monolayer capacity of methanol, mmol/g, NA- the number of Avogadro, mmol-1, Sch - value landing a molecule of methanol, 0.25·10-18m2according to the generally accepted view (see, for example, Apokryphos. Adsorption methods for the measurement of specific surface area and structure of the pores of the catalysts // Kinetics and catalysis. - 1962. - V.3, № 3. - C-598).

Based on the model of non-intersecting cylindrical pores, the average pore diameter of Dcp(in nm)formed in the sample mesoporous material based on titanium dioxide was determined from the relation (see ibidem)

Dcp=4·109Vs/Sbeats,

where Sbeats. - the previously obtained value of the specific surface of the sample mesoporous material based on titanium dioxide, m2/g, Vs=and·Vo- maximum sorption pore volume, m3/g, a specific weight adsorption method using the above-described vacuum at temperature 20°and the pressure in the cavity, equal to the saturated vapor pressure of methanol, and the previously obtained under the same experimental conditions, the maximum amount of adsorption (mmol/g) of methanol, Vo- the molar volume of liquid methanol, equal 4,05·10-8m3/mmol.

X-ray phase analysis of the samples mesoporous material based on titanium dioxide on the content of the crystalline phase of anatase were performed on the diffractometer DRON-3M, using copper, filtered Nickel radiation at a voltage of 30 kV and current of 20 mA, the cracks when shooting in the small-angle region 1,0-1,0-0,5, in the middle and far fields of angles - 2,0-2,0-1,0 (see, for example, Lierin. Handbook of x-ray structural analysis of polycrystals. - M.: State. publishing house of physical and physical-Mat. literature, 1961. - 863 C. or Weegee. XRD identification of minerals. - M.: Gosgeoltechizdat, 1957. - 868 C.). The content of anatase in the mesoporous material based on titanium dioxide was determined by the relative intensity of the characteristic reflexes at 2θ =25,4° in comparison with the sample dispersed material brand Degussa P25 company Degussa, the content of anatase in which it is known.

Photocatalytic activity of the samples mesoporous material based on titanium dioxide was evaluated by well-known methods (see, for example, Kryukov A.I., Korjak AV, Sciences-o.n.frolova SJ Photocatalytic production of hydrogen in an alcohol solution of titanium tetrachloride // Theoret. and experimental. chemistry. - 1984. - t.20, No. 2. - S-177). To do this in a glass reactor was placed 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. With constant stirring the suspension at a temperature of 40°it was irradiated with light of a mercury lamp high pressure type DRSH-1000, highlighting using a glass filter UFS-2 rays with a wavelength of about 360 nm. The total number of quanta absorbed the reaction system per unit time (I, Einstein/min or mol-quantum/min)was determined ferrioxalate chemical actinometer using the following dependency:

I=nFe(II)/Fe,

where nFe(II)- the number of ions of iron (II)formed by irradiation of a solution of ferrioxalate, fe- valued quantum yield for the formation of iron (II) for a given wavelength of radiation.

Using the obtained value of I, was calculated kVA is preset outputs f H2photocatalytic reactions allocation of molecular hydrogen from water-alcohol mixtures in the presence of the samples of the composite Nickel-semiconductor mesoporous material based on titanium dioxide:

FH2=2mH2/I,

where mH2- the rate of formation of molecular hydrogen in mol/min, which was determined by the chromatographic method.

Example 2

As an organic template for the synthesis of mesoporous material based on titanium dioxide used examanation connection tetramethyl-12-crown-4 General formula C12H24O4as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 7 wt.%. In one glass poured into 170 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 0,141 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2 hours prior to the formation of a mixture of Zola. The temperature of the mixture is at this stage of the synthesis was supported by about 25° C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat supported about 25°C and relative humidity of 65% using a saturated solution of sodium nitrite. The contact of the mixture with water vapor at this temperature provided within 14 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave where the temperature is 175°it was hydrothermally treated within 48 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 500°C for 5 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml 0,22%aqueous solution of Nickel chloride. Stirring the mixture dioxide Titus is and was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 38 wt.%, Nickel in the amount of 2.0 wt.%, had a porous structure with an average pore diameter of Dcp=9,1 nm and a specific surface area of Sbeats=85 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,091.

Example 3

As an organic template for the synthesis of mesoporous material based on titanium dioxide used axemaker the cyclic compound dibenzo-18-crown-6 the General formula C 20H24About6as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 6.5 wt.%. In one glass poured into 175 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it is 0.135 g of the template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2.5 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 20°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature using thermostat was supported by about 20°C and relative humidity of 65% using a saturated solution of ammonium nitrate. The contact of the mixture with water vapor at this temperature provided within 17 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave, where t is mperature 180° With her was hydrothermally treated for 45 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 500°C for 5 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml 0,055%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. On the Le of this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 55 wt.%, Nickel in the amount of 0.5 wt.%, had a porous structure with an average pore diameter of Dcp=9,5 nm and a specific surface area of Sbeats=76 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,092.

Example 4

As an organic template for the synthesis of mesoporous material based on titanium dioxide used examanation connection dibenzo-30-crown-10 General formula C28H40O10as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 5 wt.%. In one glass poured into 180 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 0,042 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution so the lats under vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 1.5 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 30°C. After saleabration stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature using thermostat was supported by about 30°C and relative humidity of 85% using a saturated solution of potassium chloride. The contact of the mixture with water vapor at this temperature provided within 12 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave where the temperature is 185°it was treated hydrothermally for 43 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 500°C for 5 hours to remove the template. The result has been 7,5 misopristol titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml of 0.16%-aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 55 wt.%, Nickel in the amount of 1.5 wt.%, had a porous structure with an average pore diameter of Dcp=9,3 nm and a specific surface area of Sbeats=70 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite n the Kel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction f H2=0,114.

Example 5

As an organic template for the synthesis of mesoporous material based on titanium dioxide used oxazaborolidine connection 18-Coronata-2-oxa-4 General formula C12H26About4N2as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 7 wt.%. In one glass poured 167 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 0,098 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2.5 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 25°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat supported about 25°C and a relative humidity of 62% using a saturated solution of ammonium nitrate. The contact of the mixture with water vapor at this temperature to ensure ivali within 15 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave where the temperature is 175°it was hydrothermally treated for 50 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 500°With over 4.5 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml 0,079%aqueous solution of Nickel sulfate. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 3 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and by methods which, shown in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 47 wt.%, Nickel in an amount of 0.6 wt.%, had a porous structure with an average pore diameter of Dcp=8,5 nm and a specific surface area of Sbeats=78 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,090.

Example 6

As an organic template for the synthesis of mesoporous material based on titanium dioxide used oxazaborolidine connection 18-Coronata-1-oxa-5 the General formula C12H25O5N, as a precursor of tetrapropoxide titanium General formula (C3H7O)4Ti, as a water-alcohol solvent is n-propanol containing water in an amount of 5 wt.%. In one glass poured 141 ml of this aqueous-alcoholic solvent. At room temperature astoral it 0,197 g template. In another glass beaker pour 40 ml of the same solvent. At room temperature, was dissolved in it 21 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 3 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 15°C. After saleabration stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat supported about 15°C and a relative humidity of 81% using a saturated solution of ammonium sulfate. The contact of the mixture with water vapor at this temperature provided during the 18 days before the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave where the temperature is 165°it was treated hydrothermally for 52 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous dioxide Titus is on the dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 600°C for 4 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml 0,167%aqueous solution of Nickel bromide. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 42 wt.%, Nickel in the amount of 0.9 wt.%, had a porous with whom ructure with an average pore diameter of D cp=8,9 nm and a specific surface area of Sbeats=72 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,092.

Example 7

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex examenregeling connection tetramethyl-12-crown-4 with ion lithium General formula [Li(C12H24O4)]Cl·3H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in the amount of 4 wt.%. In one glass poured 166 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 0,426 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by the Colo 25° C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat supported about 25°C and a relative humidity of 62% using a saturated solution of ammonium nitrate. The contact of the mixture with water vapor at this temperature provided within 13 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave where the temperature is 100°it was treated hydrothermally for 56 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 350°C for 7.5 hours to complete removal of the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml of 0.15%aqueous solution of Nickel chloride. Stirring the mixture dioxide ti is Ana was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 50 wt.%, Nickel in the amount of 1.4 wt.%, had a porous structure with an average pore diameter of Dcp=6,8 nm and a specific surface area of Sbeats=104 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,106.

Example 8

As an organic template for the synthesis of mesoporous material based on titanium dioxide used the comp is CEN examenregeling connection tetramethyl-12-crown-4 with potassium ion General formula [K(C 12H24O4)]J·2H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in the amount of 6 wt.%. In one glass poured 171 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 1,375 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2.5 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 20°C. After saleabration stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature using thermostat was supported by about 20°C and relative humidity of 65% using a saturated solution of sodium nitrite. The contact of the mixture with water vapor at this temperature provided during the 16 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother liquor was placed in autocl is, where at a temperature of 100°it was treated hydrothermally for 57 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 450°With over 4.5 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml of 0.18%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light rautalampi within 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 56 wt.%, Nickel in the amount of 1.7 wt.%, had a porous structure with an average pore diameter of Dcp=8,5 nm and a specific surface area of Sbeats=94 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=to 0.108.

Example 9

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex examenregeling connection tetramethyl-12-crown-4 with potassium ion General formula [K(C12H24O4)]J·2H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in the amount of 6 wt.%. In one glass poured 171 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 1,375 g template. In another glass beaker Nali is Ali 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2.5 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 20°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature using thermostat was supported by about 20°C and relative humidity of 65% using a saturated solution of sodium nitrite. The contact of the mixture with water vapor at this temperature provided during the 16 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave where the temperature is 100°it was treated hydrothermally for four days. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant. To obtain mesoporous titanium dioxide dry powder patterns were covered in glass. When the intensive stirring into a beaker were added the necessary, specified in example 1, the amount of pre-heated to the boiling point of ethyl alcohol according to the method described in example 1, the extraction was removed from the structure of the organic template. After getimplfileline structure was separated by filtration from the suspension of solid phase. It was dried up to almost complete removal of solvent. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml 0,371%aqueous solution of Nickel bromide. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 3 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried to achieve post what annoy mass.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 32 wt.%, Nickel in the amount of 2.0 wt.%, had a porous structure with an average pore diameter of Dcp=5,8 nm and a specific surface area of Sbeats=71 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,090.

Example 10

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex examenregeling connection tetramethyl-12-crown-4 with potassium ion General formula [K(C12H24O4)]J·2H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in the amount of 6 wt.%. In one glass poured 171 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 1,375 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After TRG is how the whole portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2.5 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 20°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature using thermostat was supported by about 20°C and relative humidity of 65% using a saturated solution of sodium nitrite. The contact of the mixture with water vapor at this temperature provided during the 16 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template. Formed structure was separated by filtration from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 450°C for 5.5 hours to complete removal of the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml 0,090%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. ICSID titanium, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 53 wt.%, Nickel in a quantity of 0.8 wt.%, had a porous structure with an average pore diameter of Dcp=7,3 nm and a specific surface area of Sbeats=91 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,103.

Example 11

As an organic template for the synthesis of mesoporous material based on titanium dioxide used the complex of oximetric Kochetkova connection tetramethyl-12-crown-4 with ion sodium General formula [Na(C 12H24O4)]Cl·3H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 6.5 wt.%. In one glass poured into 175 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 2,195 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 3 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 15°C. After saleabration stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat supported about 15°C and a relative humidity of 76% using a saturated solution of sodium chloride. The contact of the mixture with water vapor at this temperature provided for 19 days before the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother liquor was placed in autocl is, where at a temperature of 175°it was hydrothermally treated within 48 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 500°C for 5 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml of 0.18%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light mercury is any within 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 64 wt.%, Nickel in the amount of 1.7 wt.%, had a porous structure with an average pore diameter of Dcp=12,5 nm and a specific surface area of Sbeats=115 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,114.

Example 12

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex examenregeling connection tetramethyl-12-crown-4 with ion rubidium General formula [Rb(C12H24O4)]Br·3H2O as a precursor - tetrapropoxide titanium General formula (C3H7O)4Ti, as a water-alcohol solvent is n-propanol containing water in an amount of 5.5 wt.%. In one glass poured 145 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 0,612 g template. In another hundred glass is an poured into 40 ml of the same solvent. At room temperature, was dissolved in it 21 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 30°C. After saleabration stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature using thermostat was supported by about 30°C and relative humidity of 60% using a saturated solution of ammonium nitrate. The contact of the mixture with water vapor at this temperature provided within 14 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave, where at a temperature of 150°it was treated hydrothermally for 54 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in the portfolio oven, where the structure was caliciviral at a temperature of 500°With over 4.5 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml 0,144%aqueous solution of Nickel sulfate. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 3 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 61 wt.%, Nickel in the amount of 1.1 wt.%, had a porous structure with an average diameter of the EOS D cp=12,1 nm and a specific surface area of Sbeats=110 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,109.

Example 13

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex examenregeling connection tetramethyl-12-crown-4 with ion cesium General formula [Cs(C12H24O4)]NO3·3H2O as a precursor - tetrapropoxide titanium General formula (C3H7O)4Ti, as a water-alcohol solvent is n-propanol containing water in the amount of 4.5 wt.%. In one glass poured 136 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 0,656 g template. In another glass beaker pour 40 ml of the same solvent. At room temperature, was dissolved in it 21 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2.5 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis of p is derival about 25° C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat supported about 25°C and a relative humidity of 75% using a saturated solution of sodium chloride. The contact of the mixture with water vapor at this temperature provided within 17 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave where the temperature is 100°it was treated hydrothermally for 58 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 550°C for 5 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml of 0.37%aqueous solution of Nickel bromide. Stirring the mixture dioxide Titus is and was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 45 wt.%, Nickel in the amount of 2.0 wt.%, had a porous structure with an average pore diameter of Dcp11,3 nm and a specific surface area of Sbeats=87 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,092.

Example 14

As an organic template for the synthesis of mesoporous material based on titanium dioxide used the comp is CEN examenregeling connection tetramethyl-12-crown-4 with the magnesium ion of the General formula [Mg(C 12H24O4)]SO4·4H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 6.5 wt.%. In one glass poured into 180 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 0,570 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 3.5 hours before the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 14°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat maintained at about 14°C and a relative humidity of 69% using a saturated solution of ammonium nitrate. The contact of the mixture with water vapor at this temperature provided within 20 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template. Formed structure was separated by filtration from the mother plants is ora, dried up to almost complete removal of the solvent, and then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 450°C for 5.5 hours to complete removal of the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml to 0.19%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried to achieve constant the assy.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 55 wt.%, Nickel in an amount of 1.8 wt.%, had a porous structure with an average pore diameter of Dcp=9,1 nm and a specific surface area of Sbeats=77 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,110.

Example 15

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex examenregeling connection tetramethyl-12-crown-4 with calcium ion General formula [Ca(C12H24O4)]Cl2·3H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 5.5 wt.%. In one glass poured 166 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 0,530 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of precursors as the whole portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 30°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature using thermostat was supported by about 30°C and relative humidity 80% using a saturated solution of ammonium sulfate. The contact of the mixture with water vapor at this temperature provided within 12 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave where the temperature is 170°it was treated hydrothermally for 49 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 500°With over 4.5 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide is crushed in the dispersant, then transferred to a glass beaker. There was added 150 ml 0,22%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 52 wt.%, Nickel in the amount of 2.0 wt.%, had a porous structure with an average pore diameter of Dcp=9,3 nm and a specific surface area of Sbeats=77 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on dioxide Titus is provided on the quantum yield of the reaction f H2=0,112.

Example 16

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex examenregeling connection tetramethyl-12-crown-4 with ion strontium General formula [Sr(C12H24O4)]Cl2·3H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 7 wt.%. In one glass poured 181 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 0,601 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 30°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature using thermostat was supported by about 30°C and a relative humidity of 63% using a saturated solution of sodium nitrite. Contact smasis water vapor at this temperature provided within 14 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave where the temperature is 100°it was treated hydrothermally for 55 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 500°With over 4.5 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml of 0.16%-aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and the method is shown in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 52 wt.%, Nickel in the amount of 1.5 wt.%, had a porous structure with an average pore diameter of Dcp=9,7 nm and a specific surface area of Sbeats=94 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,103.

Example 17

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex examenregeling connection tetramethyl-12-crown-4 with ion barium General formula [Ba(C12H24O4)]Cl2·3H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 7 wt.%. In one glass poured 174 ml of this aqueous-alcoholic solvent. Pikantnoi temperature dissolved therein 0,338 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 1.5 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 35°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat supported about 35°C and a relative humidity of 62% using a saturated solution of sodium nitrite. The contact of the mixture with water vapor at this temperature provided within 12 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave where the temperature is 100°it was treated hydrothermally for 54 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain a mesoporous oxide of Titus is as dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 600°C for 4 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml 0,22%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 35 wt.%, Nickel in the amount of 2.0 wt.%, had a porous with whom ructure with an average pore diameter of D cp=10,8 nm and a specific surface area of Sbeats=89 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,092.

Example 18

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex examenregeling connection tetramethyl-12-crown-4 with ion lanthanum General formula [La(C12H24O4)]Cl3·3H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4·Ti, as a water-alcohol solvent is n-butanol containing water in the amount of 6 wt.%. In one glass poured 184 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 0,708 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage SinTe is and was supported by about 25° C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat supported about 25°C and a relative humidity of 75% using a saturated solution of sodium chloride. The contact of the mixture with water vapor at this temperature provided within 14 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave where the temperature is 100°it was treated hydrothermally in 53 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 500°C for 5 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml of 0.30%aqueous solution of Nickel bromide. Stirring the mixture dioxide Titus is and was treated with a solution of this salt for 3 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 51 wt.%, Nickel in the amount of 1.6 wt.%, had a porous structure with an average pore diameter of Dcp=12,8 nm and a specific surface area of Sbeats=119 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,104.

Example 19

As an organic template for the synthesis of mesoporous material based on titanium dioxide used whom the Lex examenregeling connection tetramethyl-12-crown-4 with ion cerium General formula [CE(C 12H24O4)]Cl3·3H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 5.5 wt.%. In one glass poured 163 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 0,355 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2.5 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 20°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature using thermostat was supported by about 20°C and a relative humidity of 76% using a saturated solution of sodium chloride. The contact of the mixture with water vapor at this temperature provided within 15 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed is in the autoclave, where at a temperature of 175°it was treated hydrothermally for 49 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 500°With over 4.5 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml 0,22%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light rautalampi within 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 61 wt.%, Nickel in the amount of 2.0 wt.%, had a porous structure with an average pore diameter of Dcp=a 13.3 nm and a specific surface area of Sbeats=117 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,113.

Example 20

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex examenregeling connection dibenzo-18-crown-6 with lithium ion General formula [Li(C20H24O6)]Cl·C2H5OH, as a precursor - tetrapropoxide titanium General formula (C3H7O)4Ti, as a water-alcohol solvent is n-amyl alcohol containing water in the amount of 4.5 wt.%. In one glass poured into 210 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 3,609 g template. In other Stekla the hydrated glass is poured into 55 ml of the same solvent. At room temperature, was dissolved in it 21 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 25°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat supported about 25°C and relative humidity 80% using a saturated solution of ammonium sulfate. The contact of the mixture with water vapor at this temperature provided during the 16 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave where the temperature is 175°it was treated hydrothermally for 46 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in felou oven, where the structure was caliciviral at a temperature of 350°C for 6.5 hours to complete removal of the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml of 0.20%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 45 wt.%, Nickel in the amount of 1.9 wt.%, had a porous structure with an average diameter of the D cp=10,9 nm and a specific surface area of Sbeats=139 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,093.

Example 21

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex examenregeling connection dibenzo-18-crown-6 with sodium ion General formula [Na(C20H24O6)]Cl·3H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 7 wt.%. In one glass poured into 170 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 3,451 g template, then 0,115 g of lanthanum chloride. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template and salts of lanthanum with vigorous stirring was introduced dropwise a solution of the precursor. After all portion of this solution was introduced into the solution template and salts of lanthanum, the resulting mixture was continued to stir for 2 hours prior to the formation of a mixture of Zola. Tempera is ur mix at this stage of the synthesis was supported by about 25° C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat supported about 25°C and relative humidity of 65% using a saturated solution of sodium nitrite. The contact of the mixture with water vapor at this temperature provided within 14 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave where the temperature is 175°it was hydrothermally treated within 48 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 500°C for 5 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml 0,22%aqueous solution of Nickel chloride. Stirring the mixture dioxide Titus is and was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 90 wt.%, Nickel in the amount of 2.0 wt.%, had a porous structure with an average pore diameter of Dcp=13,8 nm and a specific surface area of Sbeats=130 m2/, it also contained lanthanum in an amount of about 0,011 g per g of substance. As the catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide ensure maximum quantum yield of the reaction fH2=0,130.

Example 22

In ka is este organic template for the synthesis of mesoporous material based on titanium dioxide used complex examenregeling connection dibenzo-18-crown-6 with potassium ion General formula [K(C 20H24O6)]J·2H2O as a precursor - tetrapropoxide titanium General formula (C3H7O)4Ti, as a water-alcohol solvent is methanol containing water in an amount of 6.5 wt.%. In one glass poured into 100 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 8,205 g template, then 0,798 g of lanthanum chloride. In another glass beaker was poured to 50 ml of the same solvent. At room temperature, was dissolved in it 21 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of precursor salts of lanthanum. After all portion of this solution was introduced into the solution template, the resulting mixture was continued to stir for 3 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 15°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat supported about 15°C and a relative humidity of 69% using a saturated solution of ammonium nitrate. The contact of the mixture with water vapor at this temperature provided during the 16 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the exact solution was placed in an autoclave, where at a temperature of 175°it was hydrothermally treated for 50 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 450°C for 5.5 hours to complete removal of the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml of 0.17%-aqueous solution of Nickel sulfate. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 3 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light Rtut the th lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 71 wt.%, Nickel in the amount of 1.3 wt.%, had a porous structure with an average pore diameter of Dcp=11,3 nm and a specific surface area of Sbeats=119 m2/, it also contained lanthanum in an amount of about 0,018 g per g of substance. As the catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,111.

Example 23

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex examenregeling connection dibenzo-18-crown-6 with ion rubidium General formula [Rb(C20H24O6)]Br·3H2O as a precursor-tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in the amount of 6 wt.%. In one glass poured into 180 ml of this aqueous alcoholic solvent At room temperature was dissolved in it 8,467 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise, a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 25°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat supported about 25°C and a relative humidity of 75% using a saturated solution of sodium chloride. The contact of the mixture with water vapor at this temperature provided within 15 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave where the temperature is 175°it was treated hydrothermally for 49 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain a mesoporous oxide of Titus is as dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 500°C for 5 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml of 0.09%-aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 75 wt.%, Nickel in a quantity of 0.8 wt.%, had a porous with whom ructure with an average pore diameter of D cp=12,0 nm and a specific surface area of Sbeats=121 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,112.

Example 24

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex examenregeling connection dibenzo-18-crown-6 with ion cesium General formula [Cs(C20H24O6)]NO3·2H2O as a precursor - tetraethoxy titanium General formula (C2H5O)4Ti, as a water-alcohol solvent is ethanol containing water in an amount of 5 wt.%. In one glass poured into 120 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 4,317 g template. In another glass beaker was poured in 32 ml of the same solvent. At room temperature, was dissolved in it 18 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 4 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis supported is about 10° C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat maintained about 10°C and a relative humidity of 73% using a saturated solution of ammonium nitrate. The contact of the mixture with water vapor at this temperature provided for 19 days before the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave where the temperature is 100°it was treated hydrothermally in 53 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 550°C for 5 hours to remove the template. The result obtained 7.9 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 158 ml 0,17%aqueous solution of Nickel chloride. Stirring the mixture dioxide Titus who was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 72 wt.%, Nickel in the amount of 1.6 wt.%, had a porous structure with an average pore diameter of Dcp=of 9.2 nm and a specific surface area of Sbeats=90 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,123.

Example 25

As an organic template for the synthesis of mesoporous material based on titanium dioxide used the comp is CEN examenregeling connection dibenzo-18-crown-6 with magnesium ion General formula [Mg(C 20H24O6)]SO4·4H2Oh, as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 6.5 wt.%. In one glass poured 177 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 4,040 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2.5 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 25°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat supported about 25°C and a relative humidity of 75% using a saturated solution of sodium chloride. The contact of the mixture with water vapor at this temperature provided during the 16 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed is in the autoclave, where at a temperature of 200°it was treated hydrothermally for 51 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 600°C for 4 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml of 0.20%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury l is the IPA for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 77 wt.%, Nickel in the amount of 1.9 wt.%, had a porous structure with an average pore diameter of Dcp=12,9 nm and a specific surface area of Sbeats=115 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,122.

Example 26

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex examenregeling connection dibenzo-18-crown-6 with calcium ion General formula [CA(C20H24O6)]Cl2·3H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 7 wt.%. In one glass poured 183 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 3,834 g template. In another glass the TACAN poured into 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 30°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature using thermostat was supported by about 30°C and relative humidity 80% using a saturated solution of ammonium sulfate. The contact of the mixture with water vapor at this temperature provided within 13 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave where the temperature is 175°it was treated hydrothermally for 49 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in felou oven, where the structure was caliciviral at a temperature of 500°With over 4.5 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml of 0.14%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 58 wt.%, Nickel in the amount of 1.3 wt.%, had a porous structure with an average diameter of the D cp=10,6 nm and a specific surface area of Sbeats=157 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,111.

Example 27

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex examenregeling connection dibenzo-18-crown-6 with ion strontium General formula [Sr(C20H24O6)]Cl2·3H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 5 wt.%. In one glass poured 172 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 0,859 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis supported is about 30° C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature using thermostat was supported by about 30°C and a relative humidity of 75% using a saturated solution of sodium chloride. The contact of the mixture with water vapor at this temperature provided within 14 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave where the temperature is 175°it was treated hydrothermally for 47 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 400°C for 5.5 hours to complete removal of the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml of 0.07%aqueous solution of Nickel chloride. Stirring the mixture dioxide Titus who was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 62 wt.%, Nickel in an amount of 0.6 wt.%, had a porous structure with an average pore diameter of Dcp=12,2 nm and a specific surface area of Sbeats=127 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,107.

Example 28

As an organic template for the synthesis of mesoporous material based on titanium dioxide used whom the Lex examenregeling connection dibenzo-18-crown-6 with ion barium General formula [VA(C 20H24O6)]Cl2·3H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 5.5 wt.%. In one glass poured 162 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 0,934 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 3 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 20°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature using thermostat was supported by about 30°C and a relative humidity of 75% using a saturated solution of sodium chloride. The contact of the mixture with water vapor at this temperature provided within 17 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed is in the autoclave, where at a temperature of 175°it was treated hydrothermally for 46 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 600°C for 4 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml of 0.18%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light mercury is any within 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 73 wt.%, Nickel in the amount of 1.7 wt.%, had a porous structure with an average pore diameter of Dcp=14,3 nm and a specific surface area of Sbeats=107 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,120.

Example 29

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex examenregeling connection dibenzo-18-crown-6 with lanthanum ion General formula [La(C20H24O6)]Cl3·3H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in the amount of 4.5 wt.%. In one glass poured into 175 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 4,703 g template. In another glass the TACAN poured into 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 3.5 hours before the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 17°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat maintained at about 17°C and relative humidity of 65% using a saturated solution of sodium nitrite. The contact of the mixture with water vapor at this temperature provided within 20 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave where the temperature is 175°it was hydrothermally treated within 48 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in the portfolio oven, where the structure was caliciviral at a temperature of 470°C for 5 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml of 0.20%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 81 wt.%, Nickel in the amount of 1.9 wt.%, had a porous structure with an average diameter D cp=13,7 nm and a specific surface area of Sbeats=125 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,125.

Example 30

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex examenregeling connection dibenzo-18-crown-6 with cerium ion General formula [CE(C20H24O6)]Cl3·3H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in the amount of 6 wt.%. In one glass poured 185 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 2,356 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 3 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis support is supported about 20° C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature using thermostat was supported by about 20°C and a relative humidity of 76% using a saturated solution of sodium chloride. The contact of the mixture with water vapor at this temperature provided within 17 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave where the temperature is 175°it was treated hydrothermally for 46 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 500°With over 4.5 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml of 0.07%aqueous solution of Nickel chloride. Stirring the mixture dioxide Titus who was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 70 wt.%, Nickel in an amount of 0.6 wt.%, had a porous structure with an average pore diameter of Dcp=14,8 nm and a specific surface area of Sbeats=122 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,115.

Example 31

As an organic template for the synthesis of mesoporous material based on titanium dioxide used whom the Lex examenregeling connection dibenzo-30-crown-10 with ion lithium General formula [Li(C 28H40O10)]Br·3H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 7 wt.%. In one glass poured 193 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 4,941 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 30°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature using thermostat was supported by about 30°C and a relative humidity of 75% using a saturated solution of sodium chloride. The contact of the mixture with water vapor at this temperature provided within 14 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother liquor was placed in autocl is, where at a temperature of 100°it was treated hydrothermally for 56 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 350°C for 5.5 hours to complete removal of the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml 0,22%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light rautalampi within 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 40 wt.%, Nickel in the amount of 2.0 wt.%, had a porous structure with an average pore diameter of Dcp=10,8 nm and a specific surface area of Sbeats=118 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,092.

Example 32

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex examenregeling connection dibenzo-30-crown-10 with potassium ion General formula [K(C28H40O10)]J·2H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 5.7 wt.%. In one glass poured into 175 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 5,392 g template. In another glass beaker Nali is Ali 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 30°C. After saleabration stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature using thermostat was supported by about 30°C and relative humidity 80% using a saturated solution of ammonium sulfate. The contact of the mixture with water vapor at this temperature provided within 13 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave, where temperatures up to 180°it was treated hydrothermally for 52 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in felou oven, where the structure was caliciviral at a temperature of 500°C for 5 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml 0,22%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 52 wt.%, Nickel in the amount of 2.0 wt.%, had a porous structure with an average diameter D cp=16 nm and a specific surface area of Sbeats=122 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,107.

Example 33

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex examenregeling connection dibenzo-30-crown-10 with ion sodium General formula [TA(C28H40About10)]Cl2·N2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 5.7 wt.%. In one glass poured 168 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 4,606 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of synthesis supports rivali about 25° C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat supported about 25°C and relative humidity 80% using a saturated solution of ammonium sulfate. The contact of the mixture with water vapor at this temperature provided during the 16 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave where the temperature is 100°it was treated hydrothermally for 57 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 400°C for 6 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml to 0.19%aqueous solution of Nickel chloride. Stirring the mixture dioxide ti is Ana was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 70 wt.%, Nickel in an amount of 1.8 wt.%, had a porous structure with an average pore diameter of Dcp=10,6 nm and a specific surface area of Sbeats=112 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,124.

Example 34

As an organic template for the synthesis of mesoporous material based on titanium dioxide used whom the Lex examenregeling connection dibenzo-30-crown-10 with the ion rubidium General formula [Rb(C 28H40O10)]Br·3H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in the amount of 6 wt.%. In one glass poured 146 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 1,134 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 4 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 15°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat supported about 15°C and a relative humidity of 69% using a saturated solution of ammonium nitrate. The contact of the mixture with water vapor at this temperature provided for 19 days before the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother liquor was placed in autocl is in, where at a temperature of 170°it was treated hydrothermally for 56 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 350°C for 6.5 hours to complete removal of the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml of 0.10%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light rautalampi within 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 66 wt.%, Nickel in the amount of 0.9 wt.%, had a porous structure with an average pore diameter of Dcp=11,4 nm and a specific surface area of Sbeats=142 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,116.

Example 35

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex examenregeling connection dibenzo-24-crown-6 with ion cesium General formula [Cs(C24H32O8)]NO3·4H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-hexyl alcohol containing water in an amount of 6.5 wt.%. In one glass poured 246 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 1,073 g template. In the other stack is regular glass poured 74 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 4 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 25°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat supported about 25°C and a relative humidity of 75% using a saturated solution of sodium chloride. The contact of the mixture with water vapor at this temperature provided within 15 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave, where at a temperature of 150°it was treated hydrothermally for 58 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in mu is entrusted oven, where the structure was caliciviral at a temperature of 500°C for 5 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml of 0.18%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 72 wt.%, Nickel in the amount of 1.7 wt.%, had a porous structure with an average diameter D cp=12,7 nm and a specific surface area of Sbeats=90 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,125.

Example 36

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex examenregeling connection dibenzo-30-crown-10 with the ion magnesium General formula [Mg(C28H40About10)]SO4·4H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 5.5 wt.%. In one glass poured 176 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 1,092 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis under arrival about 35° C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat supported about 35°C and relative humidity 80% using a saturated solution of ammonium sulfate. The contact of the mixture with water vapor at this temperature provided within 12 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave where the temperature is 175°it was treated hydrothermally for 57 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 500°C for 5 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml of 0.16%-aqueous solution of Nickel chloride. Stirring the mixture dioxide ti is Ana was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 65 wt.%, Nickel in the amount of 1.5 wt.%, had a porous structure with an average pore diameter of Dcp=15,7 nm and a specific surface area of Sbeats=129 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,115.

Example 37

As an organic template for the synthesis of mesoporous material based on titanium dioxide used whom the Lex examenregeling connection dibenzo-30-crown-10 with the calcium ion of the General formula [Ca(C 28H40O10)]Cl2·3H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 7 wt.%. In one glass poured 198 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 5,120 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 30°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature using thermostat was supported by about 30°C and a relative humidity of 63% using a saturated solution of sodium nitrite. The contact of the mixture with water vapor at this temperature provided within 14 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed autoclave, where at a temperature of 175°it was treated hydrothermally for 58 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 600°C for 4 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml of 0.08%-aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light mercury is any within 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 52 wt.%, Nickel in the amount of 0.7 wt.%, had a porous structure with an average pore diameter of Dcp=15,0 nm and a specific surface area of Sbeats=120 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,103.

Example 38

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex examenregeling connection dibenzo-24-crown-6 with ion strontium General formula [Sr(C24H32O8)]Cl2·2H2O as a precursor - tetraethoxy titanium General formula (C2H5O)4Ti, as a water-alcohol solvent is ethanol containing water in the amount of 6 wt.%. In one glass poured 124 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 4,693 g template. In another glass stack is n poured in 32 ml of the same solvent. At room temperature, was dissolved in it 18 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 3 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 20°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature using thermostat was supported by about 2°C and a relative humidity of 75% using a saturated solution of sodium chloride. The contact of the mixture with water vapor at this temperature provided within 17 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave where the temperature is 100°it was treated hydrothermally for 56 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in mu is entrusted oven, where the structure was caliciviral at a temperature of 600°C for 4 hours to remove the template. The result obtained 7.9 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 158 ml 0,22%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added to 1.6 l of ethanol containing a 3.2 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 40 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 50 wt.%, Nickel in the amount of 2.0 wt.%, had a porous structure with an average diameter of the D cp=12,0 nm and a specific surface area of Sbeats=77 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,106.

Example 39

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex examenregeling connection dibenzo-30-crown-10 with the ion barium General formula [VA(C28H40About10)]Cl2·3H2O as a precursor - tetrapropoxide titanium General formula (C3H7O)4Ti, as a water-alcohol solvent is n-p alcohol containing water in an amount of 7 wt.%. In one glass poured into 270 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 2,915 g template. In another glass poured into 75 ml of the same solvent. At room temperature, was dissolved in it 21 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage si is thesis supported about 30° C. After saleabration stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature using thermostat was supported by about 30°C and a relative humidity of 75% using a saturated solution of sodium chloride. The contact of the mixture with water vapor at this temperature provided within 13 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave where the temperature is 155°it was treated hydrothermally for 56 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 500°With over 4.5 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml of 0.17%-aqueous solution of Nickel chloride. Stirring the mixture dioxide Titus who was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 54 wt.%, Nickel in the amount of 1.6 wt.%, had a porous structure with an average pore diameter of Dcp=11,7 nm and a specific surface area of Sbeats=89 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=is 0.102.

Example 40

As an organic template for the synthesis of mesoporous material based on titanium dioxide used the comp is CEN examenregeling connection dibenzo-24-crown-8 with ion lanthanum General formula [La(C 24H32O8)]Cl3·3H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in the amount of 6 wt.%. In one glass poured 184 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 5,349 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 30°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature using thermostat was supported by about 30°C and a relative humidity of 63% using a saturated solution of sodium nitrite. The contact of the mixture with water vapor at this temperature provided within 14 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was put in the autoclave, where at a temperature of 175°it was treated hydrothermally for 58 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 500°With over 4.5 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml 0,22%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light rautalampi within 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 70 wt.%, Nickel in the amount of 2.0 wt.%, had a porous structure with an average pore diameter of Dcp=15,2 nm and a specific surface area of Sbeats=133 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,123.

Example 41

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex examenregeling connection dibenzo-24-crown-6 with cerium ion General formula [CE(C24H32O8)]Cl3·3H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 5 wt.%. In one glass poured 192 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 5,356 g template. In the other glass with the akan poured into 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 20°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature using thermostat was supported by about 20°C and a relative humidity of 63% using a saturated solution of sodium nitrite. The contact of the mixture with water vapor at this temperature provided during the 18 days before the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave where the temperature is 175°it was treated hydrothermally for 57 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in mu is entrusted oven, where the structure was caliciviral at a temperature of 600°C for 4 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml of 0.13%-aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 65 wt.%, Nickel in the amount of 1.2 wt.%, had a porous structure with an average diameter D cp=16,0 nm and a specific surface area of Sbeats=123 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,111.

Example 42

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex examenregeling connection dibenzo-24-crown-6 with cerium ion General formula [CE(C24H32O8)]Cl3·3H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 5 wt.%. In one glass poured 192 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 5,356 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis support is supported about 20° C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature using thermostat was supported by about 20°C and a relative humidity of 63% using a saturated solution of sodium nitrite. The contact of the mixture with water vapor at this temperature provided during the 18 days before the final formation of a mixture of spatial structure of titanium dioxide/organic template. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 600°C for 4 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml 0,22%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, C is the placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 61 wt.%, Nickel in the amount of 2.0 wt.%, had a porous structure with an average pore diameter of Dcp=14,5 nm and a specific surface area of Sbeats=102 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,113.

Example 43

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex examenregeling connection dibenzo-24-crown-8 with ion cerium General formula [CE(C24H32O8)]Cl3·3H2Oh, as a precursor - tetrabutoxide titanium General formula (C4H O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 5 wt.%. In one glass poured 192 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 5,356 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 20°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature using thermostat was supported by about 20°C and a relative humidity of 63% using a saturated solution of sodium nitrite. The contact of the mixture with water vapor at this temperature provided during the 18 days before the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave, where at a temperature of 200°it was treated hydrothermally for three days. After this structure together with the exact solution was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain the required number of mesoporous titanium dioxide corresponding portion of the crushed dry mix was filled into the glass. Under vigorous stirring in a beaker were added the necessary specified in example 1, the amount of pre-heated to the boiling point of ethyl alcohol according to the method described in example 1, the extraction was removed from the structure of the organic template. After getimplfileline structure was separated by filtration from the suspension of solid phase. It was dried up to almost complete removal of the solvent, and then crushed. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml 0,22%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 the Olga water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 36 wt.%, Nickel in the amount of 2.0 wt.%, had a porous structure with an average pore diameter of Dcp=11,5 nm and a specific surface area of Sbeats=72 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,091.

Example 44

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex hexaazatetracyclo connection 18-Coronata-2-oxa-4 lithium ion General formula [Li(C12H26O4N2)]Cl·3H2Oh, as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-is ethanol, containing water in an amount of 5.5 wt.%. In one glass poured 184 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 5,232 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2.5 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 25°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat supported about 25°C and a relative humidity of 62% using a saturated solution of ammonium nitrate. The contact of the mixture with water vapor at this temperature provided during the 16 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave, where at a temperature of 200°it was treated hydrothermally in 53 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separated the structure from the mother liquor, dried up to almost complete removal of the solvent, and then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 600°C for 4 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml 0,22%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching a constant m is ssy.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 76 wt.%, Nickel in the amount of 2.0 wt.%, had a porous structure with an average pore diameter of Dcp=12,4 nm and a specific surface area of Sbeats=100 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,122.

Example 45

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex hexaazatetracyclo connection 18-Coronata-2-oxa-4 with potassium ion General formula [K(C12H26O4N2)]J·2H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 5 wt.%. In one glass poured 194 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 6,779 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. P is after all a portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 30°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature using thermostat was supported by about 30°C and a relative humidity of 63% using a saturated solution of sodium nitrite. The contact of the mixture with water vapor at this temperature provided within 15 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave, where at a temperature of 200°it was hydrothermally treated for 50 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 600°C for 4 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide from what was alkali in the dispersant, then transferred to a glass beaker. There was added 150 ml 0,22%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 74 wt.%, Nickel in the amount of 2.0 wt.%, had a porous structure with an average pore diameter of Dcp=12,7 nm and a specific surface area of Sbeats=105 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on dioxide ti the Ana provided the quantum yield of the reaction f H2=0,123.

Example 46

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex hexaazatetracyclo connection 18-Coronata-2-oxa-4 with ion sodium General formula [Na(C12H26O4N2)]Cl·3H2Oh, as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 7 wt.%. In one glass poured 204 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 5,209 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 30°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature using thermostat was supported by about 30°C and relative humidity 80% using a saturated solution of ammonium sulfate. Contact the MCA and with water vapor at this temperature provided within 13 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave, where at a temperature of 200°it was treated hydrothermally for 52 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 600°C for 4 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml to 0.19%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°according to the method, n is evidenoe in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 78 wt.%, Nickel in an amount of 1.8 wt.%, had a porous structure with an average pore diameter of Dcp=13,1 nm and a specific surface area of Sbeats=109 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,125.

Example 47

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex hexaazatetracyclo connection 18-Coronata-2-oxa-4 with ion rubidium General formula [Rb(C12H26O4N2)]Br·3H2O as a precursor - tetraethoxy titanium General formula (C2H5O)4Ti, as a water-alcohol solvent is ethanol containing water in an amount of 7 wt.%. In one glass poured into 120 ml of this aqueous-alcoholic solvent. Por the room temperature was dissolved in it 3,518 g template. In another glass beaker was poured 30 ml of the same solvent. At room temperature, was dissolved in it 18 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 3.5 hours before the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 10°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat maintained about 10°C and a relative humidity of 73% using a saturated solution of ammonium nitrate. The contact of the mixture with water vapor at this temperature provided during the 18 days before the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave where the temperature is 100°it was treated hydrothermally for 58 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous dioxide Titus is on the dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 600°C for 4 hours to remove the template. The result obtained 7.9 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 158 ml of 0.15%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added to 1.6 l of ethanol containing a 3.2 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light mercury lamps for 37 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 50 wt.%, Nickel in the amount of 1.4 wt.%, had a porous is the structure with an average pore diameter of D cp=7,9 nm and a specific surface area of Sbeats=76 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,103.

Example 48

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex hexaazatetracyclo connection 18-Coronata-2-oxa-4 with ion cesium General formula [Cs(C12H26O4N2)]NO3·3H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 5 wt.%. In one glass poured 182 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 3,733 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 3 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage SinTe is and was supported by about 15° C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat supported about 15°C and a relative humidity of 76% using a saturated solution of sodium chloride. The contact of the mixture with water vapor at this temperature provided within 17 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave where the temperature is 100°it was treated hydrothermally for 55 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 500°With over 4.5 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml 0,22%aqueous solution of Nickel chloride. Stirring the mixture dioxide Titus who was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 53 wt.%, Nickel in the amount of 2.0 wt.%, had a porous structure with an average pore diameter of Dcp=7,8 nm and a specific surface area of Sbeats=71 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,107.

Example 49

As an organic template for the synthesis of mesoporous material based on titanium dioxide used the comp is CEN hexaazatetracyclo connection 18-coronata-2-oxa-4 with the magnesium ion of the General formula [Mg(C 12H26O4N2)]SO4·3H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 5.5 wt.%. In one glass poured 168 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 3,185 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2.5 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 25°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat supported about 25°C and relative humidity of 65% using a saturated solution of sodium nitrite. The contact of the mixture with water vapor at this temperature provided within 15 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother liquor which was homesale in the autoclave, where at a temperature of 175°it was treated hydrothermally for 52 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 500°With over 4.5 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml 0,22%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light rautalampi within 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 61 wt.%, Nickel in the amount of 2.0 wt.%, had a porous structure with an average pore diameter of Dcp=9,6 nm and a specific surface area of Sbeats=92 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,114.

Example 50

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex hexaazatetracyclo connection 18-Coronata-2-oxa-4 calcium ion General formula [CA(C12H26O4N2)]Cl2·3H2Oh, as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in the amount of 4.5 wt.%. In one glass poured into 170 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 3,118 g template. In each is the first glass poured into 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2.5 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 25°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat supported about 25°C and relative humidity of 65% using a saturated solution of sodium nitrite. The contact of the mixture with water vapor at this temperature provided within 15 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave where the temperature is 175°it was treated hydrothermally in 53 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in the portfolio oven, where the structure was caliciviral at a temperature of 500°With over 4.5 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml 0,055%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from Astor Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 64 wt.%, Nickel in the amount of 0.5 wt.%, had a porous structure with an average diameter of the D cp=10,2 nm and a specific surface area of Sbeats=89 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,114.

Example 51

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex hexaazatetracyclo connection 18-Coronata-2-oxa-4 calcium ion General formula [Ca(C12H26O4N2)]Cl2·3H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in the amount of 4.5 wt.%. In one glass poured into 170 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 3,118 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2.5 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage is NASA supported about 25° C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat supported about 25°C and relative humidity of 65% using a saturated solution of sodium nitrite. The contact of the mixture with water vapor at this temperature provided within 15 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave, where at a temperature of 150°it was treated hydrothermally for four days. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain the required number of mesoporous titanium dioxide corresponding portion of the crushed dry mix was filled into the glass. Under vigorous stirring in a beaker were added the necessary specified in example 1, the amount of pre-heated to the boiling point of ethyl alcohol according to the method described in example 1, the extraction was removed from the structure of the organic template. After getimplfileline structure was separated by filtration from the suspension of solid f the memory. It was dried up to almost complete removal of the solvent, and then crushed. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml 0,22%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 34 wt.%, Nickel in the amount of 2.0 wt.%, had a porous structure with an average pore diameter of Dcp=13,2 nm and the specific surface is of S beats=73 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,090.

Example 52

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex hexaazatetracyclo connection 18-Coronata-2-oxa-4 calcium ion General formula [Ca(C12H26O4N2)]Cl2·3H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in the amount of 4.5 wt.%. In one glass poured into 170 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 3,118 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2.5 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 25°C. On the Le saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat supported about 25°C and relative humidity of 65% using a saturated solution of sodium nitrite. The contact of the mixture with water vapor at this temperature provided within 15 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template. Formed structure was separated by filtration from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 500°C for 5 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml of 0.16%-aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There W is added 1.5 liters of ethyl alcohol, containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 61 wt.%, Nickel in the amount of 1.5 wt.%, had a porous structure with an average pore diameter of Dcp=11,4 nm and a specific surface area of Sbeats=81 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,113.

Example 53

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex hexaazatetracyclo connection 18-Coronata-2-oxa-4 calcium ion General formula [Ca(C12H26O4N2)]Cl2·3H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as in the bottom-alcohol solvent n-butanol containing water in the amount of 4.5 wt.%. In one glass poured into 170 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 3,118 g template, then 0,105 g of lanthanum chloride. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template and salts of lanthanum with vigorous stirring was introduced dropwise a solution of the precursor. After all portion of this solution was introduced into the solution template and salts of lanthanum, the mixture continued to be stirred for 2.5 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 25°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat supported about 25°C and relative humidity of 65% using a saturated solution of sodium nitrite. The contact of the mixture with water vapor at this temperature provided within 15 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template. Formed structure was separated by filtration from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain m zaporizkogo titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 600°C for 4 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml of 0.20%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 60 wt.%, Nickel in the amount of 1.9 wt.%, had a porous with whom ructure with an average pore diameter of D cp=12,2 nm and a specific surface area of Sbeats=75 m2/, it also contained lanthanum in an amount of about 0,012 g per g of substance. As the catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,112.

Example 54

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex hexaazatetracyclo connection 18-Coronata-2-oxa-4 with ion strontium General formula [Sr(C12H26O4N2)]Cl2·2H2O as a precursor - tetraisopropoxide titanium General formula (C3H7O)4Ti, as a water-alcohol solvent is n-propanol containing water in an amount of 6.5 wt.%. In one glass poured 142 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 1,667 g template. In another glass beaker was poured 41 ml of the same solvent. At room temperature, was dissolved in it 21 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued re elevate for 3 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 20°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature using thermostat was supported by about 20°C and a relative humidity of 76% using a saturated solution of sodium chloride. The contact of the mixture with water vapor at this temperature provided during the 18 days before the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave where the temperature is 175°it was treated hydrothermally for 54 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 500°With over 4.5 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml of 0.2%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 69 wt.%, Nickel in the amount of 2.0 wt.%, had a porous structure with an average pore diameter of Dcp=10,9 nm and a specific surface area of Sbeats=86 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,122.

Example 55

As the organic the Lata for the synthesis of mesoporous material based on titanium dioxide used complex hexaazatetracyclo connection 18-Coronata-2-oxa-4 with ion barium General formula [Ba(C 12H26O4N2)]Cl2·3H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 5.5 wt.%. In one glass poured 177 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 1,914 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 30°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature using thermostat was supported by about 30°C and a relative humidity of 63% using a saturated solution of sodium nitrite. The contact of the mixture with water vapor at this temperature provided within 14 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution p which was memali in the autoclave, where at a temperature of 155°it was treated hydrothermally for 54 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 600°C for 4 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml of 0.16%-aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light mercury is any within 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 72 wt.%, Nickel in the amount of 1.5 wt.%, had a porous structure with an average pore diameter of Dcp=12,3 nm and a specific surface area of Sbeats=83 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,121.

Example 56

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex hexaazatetracyclo connection 18-Coronata-2-oxa-4 with ion lanthanum General formula [La(C12H26O4N2)]Cl3·7H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 7 wt.%. In one glass poured 167 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 0,928 g template. In dragosstefany glass poured into 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2.5 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 20°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature using thermostat was supported by about 20°C and a relative humidity of 81% using a saturated solution of ammonium sulfate. The contact of the mixture with water vapor at this temperature provided during the 18 days before the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave where the temperature is 175°it was treated hydrothermally for 55 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed the muffle furnace, where the structure was caliciviral at a temperature of 600°C for 4 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml of 0.17%-aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 70 wt.%, Nickel in the amount of 1.6 wt.%, had a porous structure with an average diameter D cp=12,8 nm and a specific surface area of Sbeats=97 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,122.

Example 57

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex hexaazatetracyclo connection 18-Coronata-2-oxa-4 with ion cerium General formula [CE(C12H26O4N2)]Cl3·2H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 4.7 wt.%. In one glass poured 157 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 0,794 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2.5 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the Intesa supported about 20° C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature using thermostat was supported by about 20°C and a relative humidity of 76% using a saturated solution of sodium chloride. The contact of the mixture with water vapor at this temperature provided for 19 days before the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave where the temperature is 175°it was treated hydrothermally for 54 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 600°C for 4 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml 0,22%aqueous solution of Nickel chloride. Stirring the mixture dioxide Titus is and was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 67 wt.%, Nickel in the amount of 2.0 wt.%, had a porous structure with an average pore diameter of Dcp=11.9 nm and a specific surface area of Sbeats=99 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,121.

Example 58

As an organic template for the synthesis of mesoporous material based on titanium dioxide used the comp is CEN hexaazatetracyclo connection dibenzo-18-coronata-1-oxa-5 with ion lithium General formula [Li(C 20H25About5N)]Cl·3H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 3.7 wt.%. In one glass poured 207 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 2,623 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 3 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 20°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature using thermostat was supported by about 20°C and relative humidity of 65% using a saturated solution of ammonium nitrate. The contact of the mixture with water vapor at this temperature provided during the 18 days before the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in a waveguide the keypad, where at a temperature of 200°it was treated hydrothermally for 49 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 600°C for 4 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml of 0.11%-aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light mercury is any within 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 76 wt.%, Nickel in the amount of 1.0 wt.%, had a porous structure with an average pore diameter of Dcp=13.5 nm and a specific surface area of Sbeats=119 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,113.

Example 59

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex hexaazatetracyclo connection dibenzo-18-coronata-1-oxa-5 with potassium ion General formula [K(C20H25O5N)]J·2H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 7 wt.%. In one glass poured 211 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 3,398 g template. In the other glass with the akan poured into 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2.5 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 20°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature using thermostat was supported by about 20°C and relative humidity of 65% using a saturated solution of ammonium nitrate. The contact of the mixture with water vapor at this temperature provided during the 16 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave, where at a temperature of 200°it was treated hydrothermally for 52 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in felou oven, where the structure was caliciviral at a temperature of 500°With over 4.5 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml to 0.19%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 80 wt.%, Nickel in an amount of 1.8 wt.%, had a porous structure with an average diameter of the D cp=13,8 nm and a specific surface area of Sbeats=112 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,123.

Example 60

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex hexaazatetracyclo connection dibenzo-18-coronata-1-oxa-5 with ion sodium General formula [Na(C20H25O5N)]Cl·3H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 5 wt.%. In one glass poured 191 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 2,611 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 3 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis is oderzhivali about 15° C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat supported about 15°C and a relative humidity of 81% using a saturated solution of ammonium sulfate. The contact of the mixture with water vapor at this temperature provided within 21 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave, where at a temperature of 150°it was treated hydrothermally for 49 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 600°C for 4 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml 0,055%aqueous solution of Nickel chloride. Stirring the mixture dioxide Titus who was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 78 wt.%, Nickel in the amount of 0.5 wt.%, had a porous structure with an average pore diameter of Dcp=13,0 nm and a specific surface area of Sbeats=117 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,116.

Example 61

As an organic template for the synthesis of mesoporous material based on titanium dioxide used whom the Lex hexaazatetracyclo connection dibenzo-18-coronata-1-oxa-5 with ion rubidium General formula [Rb(C 20H25O5N)]Br·3H2O as a precursor - tetraethoxy titanium General formula (C2H5O)4Ti, as a water-alcohol solvent is ethanol containing water in the amount of 4 wt.%. In one glass poured into 120 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 3,525 g template. In another glass beaker was poured 30 ml of the same solvent. At room temperature, was dissolved in it 18 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 4.5 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 10°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat maintained about 10°C and a relative humidity of 82% using a saturated solution of ammonium sulfate. The contact of the mixture with water vapor at this temperature provided within 20 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother liquor was placed in autocl is, where at a temperature of 200°it was hydrothermally treated within 48 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 600°C for 4 hours to remove the template. The result obtained 7.9 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 158 ml 0,22%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added to 1.6 l of ethanol containing a 3.2 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light rautalampi for 40 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 52 wt.%, Nickel in the amount of 2.0 wt.%, had a porous structure with an average pore diameter of Dcp=of 6.9 nm and a specific surface area of Sbeats=81 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,112.

Example 62

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex hexaazatetracyclo connection dibenzo-18-coronata-1-oxa-5 with ion cesium General formula [Cs(C20H25O5N)]NO3·3H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in the amount of 4.5 wt.%. In one glass poured 182 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 3,740 g template. In another article the glass the glass is poured into 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 5 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 10°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat maintained about 10°C and a relative humidity of 73% using a saturated solution of ammonium nitrate. The contact of the mixture with water vapor at this temperature was provided for 22 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave, where at a temperature of 150°it was hydrothermally treated for 50 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in the portfolio oven, where the structure was caliciviral at a temperature of 400°C for 6 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml of 0.15%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 58 wt.%, Nickel in the amount of 1.4 wt.%, had a porous structure with an average diameter D cp=8.3 nm and a specific surface area of Sbeats=77 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,111.

Example 63

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex hexaazatetracyclo connection dibenzo-18-coronata-1-oxa-5 with the magnesium ion of the General formula [Mg(C20H25O5N)]SO4·3H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in the amount of 4 wt.%. In one glass poured 174 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 3,193 g template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2.5 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of sin is ESA supported about 25° C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat supported about 25°C and relative humidity 80% using a saturated solution of ammonium sulfate. The contact of the mixture with water vapor at this temperature provided within 17 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave, where at a temperature of 150°it was hydrothermally treated within 48 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 500°C for 5 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml to 0.19%aqueous solution of Nickel chloride. Stirring the mixture dioxide ti is Ana was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 68 wt.%, Nickel in an amount of 1.8 wt.%, had a porous structure with an average pore diameter of Dcp=10,3 nm and a specific surface area of Sbeats=97 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,120.

Example 64

As an organic template for the synthesis of mesoporous material based on titanium dioxide used the comp is CEN hexaazatetracyclo connection dibenzo-18-coronata-1-oxa-5 with the calcium ion of the General formula [Ca(C 20H25O5N)]Cl2·3H2Oh, as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 7 wt.%. In one glass poured into 170 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 3,126 a template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2.5 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 25°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat supported about 25°C and relative humidity of 65% using a saturated solution of sodium nitrite. The contact of the mixture with water vapor at this temperature provided during the 18 days before the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed autoclave, where at a temperature of 175°it was treated hydrothermally for 46 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 600°C for 4 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml of) 0.157%aqueous solution of Nickel sulfate. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with a mercury light the lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 66 wt.%, Nickel in the amount of 1.2 wt.%, had a porous structure with an average pore diameter of Dcp=11,3 nm and a specific surface area of Sbeats=91 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,112.

Example 65

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex hexaazatetracyclo connection dibenzo-18-coronata-1-oxa-5 with ion strontium General formula [Sr(C20H25O5N)]Cl2·2H2O as a precursor - tetrapropoxide titanium General formula (C3H7O)4Ti, as a water-alcohol solvent is n-propanol containing water in an amount of 6.5 wt.%. In one glass poured 143 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 1,671 template. In the other the glass poured into 50 ml of the same solvent. At room temperature, was dissolved in it 21 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 3 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 20°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature using thermostat was supported by about 20°C and a relative humidity of 76% using a saturated solution of sodium chloride. The contact of the mixture with water vapor at this temperature provided within 20 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave where the temperature is 175°it was hydrothermally treated within 48 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in mu is entrusted oven, where the structure was caliciviral at a temperature of 400°C for 5.5 hours to complete removal of the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml 0,278%aqueous solution of Nickel bromide. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 3 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 63 wt.%, Nickel in the amount of 1.5 wt.%, had a porous structure with an average diameter of p is p D cp=to 11.6 nm and a specific surface area of Sbeats=89 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,120.

Example 66

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex hexaazatetracyclo connection dibenzo-18-coronata-1-oxa-5 with ion barium General formula [Ba(C20H25O5N)]Cl2·3H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 6.3 wt.%. In one glass poured 164 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 1,918 template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage Sint who was supported by about 30° C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature using thermostat was supported by about 30°C and a relative humidity of 63% using a saturated solution of sodium nitrite. The contact of the mixture with water vapor at this temperature provided during the 16 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave where the temperature is 125°it was treated hydrothermally in 53 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 600°C for 4 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml 0,22%aqueous solution of Nickel chloride. Stirring the mixture dioxide Titus is and was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 71 wt.%, Nickel in the amount of 2.0 wt.%, had a porous structure with an average pore diameter of Dcp=12,1 nm and a specific surface area of Sbeats=92 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,122.

Example 67

As an organic template for the synthesis of mesoporous material based on titanium dioxide used sets the COP hexaazatetracyclo connection dibenzo-18-coronata-1-oxa-5 with ion lanthanum General formula [La(C 20H25O5N)]Cl3·7H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in an amount of 5 wt.%. In one glass poured 144 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 0,929 a template. In another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2.5 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 25°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature at which a thermostat supported about 25°C and a relative humidity of 75% using a saturated solution of sodium chloride. The contact of the mixture with water vapor at this temperature provided during the 18 days before the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was put in the autoclave, where at a temperature of 185°it was treated hydrothermally for 49 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in a muffle furnace, where the structure was caliciviral at a temperature of 500°With over 4.5 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml of 0.20%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light rautalampi within 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 76 wt.%, Nickel in the amount of 1.9 wt.%, had a porous structure with an average pore diameter of Dcp=to 13.9 nm and a specific surface area of Sbeats=112 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,121.

Example 68

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex hexaazatetracyclo connection dibenzo-18-coronata-1-oxa-5 with ion cerium General formula [CE(C20H25O5N)]Cl3·2H2O as a precursor - tetrabutoxide titanium General formula (C4H9O)4Ti, as a water-alcohol solvent is n-butanol containing water in the amount of 4.5 wt.%. In one glass poured 135 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in him coefficient was 0.796 template. In another with clanny glass poured into 45 ml of the same solvent. At room temperature, was dissolved therein 25 g of the precursor. In the solution template with vigorous stirring was introduced dropwise a solution of the precursor. After all, the portion of a solution of the precursor was introduced into the solution template, the resulting mixture was continued to stir for 2 hours prior to the formation of a mixture of Zola. The temperature of the mixture at this stage of the synthesis was supported by about 30°C. After saloobrazovanie stirring of the mixture was stopped. The glass with the mixture was placed in a cell, the temperature using thermostat was supported by about 30°C and relative humidity of 85% using a saturated solution of potassium chloride. The contact of the mixture with water vapor at this temperature provided within 15 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother solution was placed in an autoclave, where at a temperature of 150°it was treated hydrothermally for 51 hours. After this structure together with the mother liquor was removed from the autoclave. Filtration separates the structure from the mother liquor, dried up almost completely remove the solvent, then crushed in the dispersant.

To obtain mesoporous titanium dioxide dry powder patterns covered in the crucible. The crucible was placed in the mansion of mu clan is inuu oven, where the structure was caliciviral at a temperature of 600°C for 4 hours to remove the template. The result was obtained 7.5 g of mesoporous titanium dioxide.

The obtained mesoporous titanium dioxide were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml 0,22%aqueous solution of Nickel chloride. Stirring the mixture of titanium dioxide was treated with a solution of this salt for 2.5 hours. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, dried to remove solvent, and then placed in a glass reactor. There was added 1.5 l of ethyl alcohol containing 3 mol of water. The mixture in the reactor was intensively stirred, heated to a temperature of about 40°and according to the method described in example 1, through a glass filter was irradiated with light of a mercury lamp for 30 minutes. After this filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then placed in a vacuum desiccator, where it was dried until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystalline phase of anatase in the amount of 72 wt.%, Nickel in the amount of 2.0 wt.%, had a porous structure with an average diameter D cp=15,7 nm and a specific surface area of Sbeats=114 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction fH2=0,124.

The examples do not exhaust all the possibilities of a practical embodiment of the inventive concept. So, in a more complex form of the inventive concept, which does not contradict the basic claims, at the stage of synthesis of mesoporous material based on titanium dioxide from saloobrazovanie before final formation from the reaction mixture of the spatial structure of the precursor/organic template the temperature of the mixture within the specified upper limit and the recommended lower limit, it is possible to maintain different, different from the one in which maintain the mixture at the previous stage of synthesis (from mixing solutions of reagents to saloobrazovanie). In addition, when the ambient temperature and humidity during the time from mixing of the reagents to the final formation from the reaction mixture of the spatial structure of the precursor/organic template changed slightly, changing these parameters in the external environment amenable forecast is in and comply with the conditions of synthesis, these stages of the synthesis of mesoporous material based on titanium dioxide can be performed without the use of a thermostat and saturated solutions of the corresponding salts.

Industrial applicability

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

1. The catalyst for photochemical reactions, which represents a mesoporous material based on titanium dioxide, characterized in that it contains a crystalline phase of anatase in the amount of not less than 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, specific surface area of not less than 70 m2/g / and as a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures provides a quantum output the response 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 0,019 g per 1 g of titanium dioxide contained in the material.

3. The method of producing catalyst for photochemical reactions, which represents a mesoporous material based on titanium dioxide, including the introduction of water-organic solvent precursor - tetraethoxide titanium and a template of organic nature, the extract of the mixture of reactants to the final formation of spatial patterns through successive stages of education Zola, and then gel, the separation of the obtained reaction product and its processing to delete a template, wherein the process is carried out in aqueous-alcoholic solvent containing not more than 7 wt.% water, as a template in a solvent is injected at least one ligand selected from the group of macrocyclic compounds, consisting of oxa - and oxazaborolidine compounds containing at least four oxygen atoms, and/or complexes of these macrocyclic 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, before the formation of Zola mixture of reagents, mix, supporting the temperature not above 35° With, before the final formation of a mixture of reagents spatial structure of the mixture is maintained at the same temperature in an open vessel under conditions of free access to the mixture of water vapor and after removal of the spatial structure of the template it is first treated with a solution of Nickel salt in a period of time sufficient to extract ions from a solution of Nickel pore structure, and then aged in a hydrogen-containing atmosphere for a time sufficient for recovery of the Nickel ions in the pore structure of the metal Nickel.

4. The method according to claim 3, characterized in that template removed from the obtained reaction product by calcining at a temperature of from 300 to 600°C.

5. 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.

6. The method according to claim 3, characterized in that template removed from the reaction product by extraction with alcohol, and the pre-reaction product is treated hydrothermally at a temperature of from 100 to 200°C.

7. The method according to claim 3, characterized in that aqueous-alcoholic solvent is further added salt of lanthanum, provided that template does not contain lanthanum ion.



 

Same patents:

Drinking water // 2286953

FIELD: food industry.

SUBSTANCE: invention relates to production of drinking water that can be used to prevent urolithiasis arising when consuming hard water saturated with magnesium salts and also osteoporosis developing at severe deficiency of calcium in body. Drinking water containing calcium in carbonate form is produced via passage of natural water having carbonate hardness at least 3 mg-equ/L through globular-structure polymer having permeability up to 8 L/min and structural matrix depicted by following formula: . Thus obtained drinking water contains calcium carbonate in soluble form easily assimilated by human body and manifesting after boiling as aragonite, whose content constitutes 60-80% of the weight of calcium carbonate.

EFFECT: improved consumer's properties of water.

2 cl, 4 dwg, 1 tbl

Drinking water // 2286953

FIELD: food industry.

SUBSTANCE: invention relates to production of drinking water that can be used to prevent urolithiasis arising when consuming hard water saturated with magnesium salts and also osteoporosis developing at severe deficiency of calcium in body. Drinking water containing calcium in carbonate form is produced via passage of natural water having carbonate hardness at least 3 mg-equ/L through globular-structure polymer having permeability up to 8 L/min and structural matrix depicted by following formula: . Thus obtained drinking water contains calcium carbonate in soluble form easily assimilated by human body and manifesting after boiling as aragonite, whose content constitutes 60-80% of the weight of calcium carbonate.

EFFECT: improved consumer's properties of water.

2 cl, 4 dwg, 1 tbl

FIELD: chemical industry; food-processing industry; medicine; chemistry of the water solutions and the water treatment.

SUBSTANCE: the invention is pertaining to the chemistry of the water solutions and the water treatment and provides for production of the conditioned seasoned drinking water of the maximum quality class received due to the source drinking water supersaturation by oxygen. The water-oxygen complexes synthesized by the chemotronic plasma in the steam-gas mixtureofH2O2 + O2 allow at commixing in the normal conditions of the steam-gas mixture with the source drinking water to produce the supersaturated by oxygen ecologically pure drinking water with the concentration of the dissolved oxygen of 10-40 mg O2/l H2O. The anomalous physical and chemical properties of the supersaturated by oxygen of the steam-gas mixture of the drinking water and the effect of increased concentration of the oxygen and their durable conservation in time of the drinking water supersaturated by oxygen state are experimentally confirmed. The invention may be used in the food-processing industry, medicine, water economies, and also in production of the butylat oxygen-containing drinking waters. The invention ensures improvement of the drinking water quality meeting the requirements of the Sanitary Rules and Standards 2.1.4.1116-02 of the Russian Federation on the vital for the people health neutral and active forms of oxygen, and, in addition the increased dates of storage of the oxygen dissolved in the conditioned drinking water.

EFFECT: the invention ensures the improved qualities of the drinking water supersaturated by oxygen.

7 dwg, 5 tbl

FIELD: disinfection of water; methods of disinfection of the natural water and the waste water.

SUBSTANCE: the invention is pertaining to the methods of disinfection of water and may be used for sterilization of the natural water and the waste water. In the chamber with water put the electrodes and exercise between them the pulsing electric discharge with formation of the electric arc. Measure the space between electrodes and keep it constant. Exercise the water running through the chamber, at that take the temperature of the water at the inlet and outlet of the chamber and keeping the given limits the values of the temperature both at the inlet and the outlet of the chamber, changing the amount of the water passing through the chamber. Provide the difference of the water temperature at the inlet and outlet of the chamber of no more than 7°C. Keep the water temperature within the limits from 5 up to 50°C. The technical result of the invention is the increase of intensity of the bactericidal action in the water.

EFFECT: the invention ensures the increase of intensity of the bactericidal action in the water.

2 cl, 1 dwg, 10 tbl, 5 ex

FIELD: chemical industry; petrochemical industry; petroleum industry; pulp-and-paper industry; mining; municipal economy; other branches of the economy; methods of electrocatalytic purification of the potable and the waste waters.

SUBSTANCE: the invention is pertaining to the method of electrocatalytic purification of the potable and the waste waters from impurities and may be used in the chemical, petrochemical, petroleum, pulp-and-paper, mining industry, the municipal utilities system, etc. The preferable field of utilization of the method is purification of the industrial waste waters and the household waste waters, the drinking waters containing the dissolved organic substances, ammonium compounds, phosphates, heavy metals and other compounds at the enterprises of petrochemical, chemical, pulp-and-paper, an oil industries, in the municipal economies, etc. Purification of the potable and the waste waters exercise by gating the water through the catalyst layer located in the inter-electrode space, where as the catalyst use the current-conductive ceramic catalyst consisting of spinels, including the ions of the metals of the variable valence. At that the purification is conducted switching on ions, thus purification lead at feeding of the oxygen of the air. The technical result of the invention is the increase of the degree of purification, intensification of the process, prevention of the catalyst destruction.

EFFECT: the invention ensures the increased degree of purification, intensification of the process, prevention of the catalyst destruction.

5 cl, 8 tbl, 10 ex

FIELD: chemical industry; methods and devices for decomposition of the organic contents of the waste water solutions.

SUBSTANCE: the invention is pertaining to the method and the device for decomposition of the organic contents of the waste water solutions. The method provides for dipping of the electrodes into the solution, creation and maintaining of the electric arc discharge between the electrodes and the electroconductive solution. The arc discharge is created by the electric current with the current density of at least 0.5 A/cm2 at the voltage of at least 70 V, and at the symmetrical alternate current with the frequency of at least 10 Hz by means of what exercise decomposition of the organic contents of the solution into the water, carbon dioxide and nitrogen. During the process maintain the optimal values of pH and-or the electroconductance of the solution. The device contains the feeding container for the source materials, at least one contour of decomposition and the container-storage. The technical result of the invention is the increased effectiveness and an environmental protection of the method.

EFFECT: the invention ensures the increased effectiveness and environmental protection of the method.

16 cl, 1 dwg, 5 tbl, 3 ex

FIELD: liquid purification equipment, in particular, liquid storage and transportation units equipped with devices for cleaning of water delivered from occasional water sources.

SUBSTANCE: liquid storage and transportation apparatus has chassis 1, platform 2 fixed on chassis, liquid reservoir mounted on platform and equipped with partitions for dividing it into parts. Part 3 for basic liquid is communicating with liquid intake part 4, and part 5 for purified liquid is communicating with liquid discharge device 9. Liquid reservoir has liquid purification and disinfection system connected with part 3 of basic liquid reservoir and consisting of filtration unit and liquid disinfection unit. Apparatus is further equipped with liquid filtration and disinfection control unit 6 and additional filter 11 mounted within liquid discharge device 9. Part 3 for basic liquid is divided into two sections, one of said sections being reservoir 12 for accumulation of preliminarily purified liquid. Liquid disinfection unit consists of disinfecting members 13 and is communicating with reservoirs for basic liquid, preliminarily purified liquid and purified liquid, and with unit 6 for controlling of liquid filtration and disinfection processes. Filtering unit consists of filtering members 14 communicating with reservoirs for basic liquid, preliminarily purified liquid, and purified liquid.

EFFECT: increased efficiency in disinfecting of water delivered from any natural water supply source.

5 cl, 1 dwg

FIELD: separation.

SUBSTANCE: vertical settler comprises discharging pipes (7) connected to the top outlet funnel (6) of cyclone (3) for peripheral zonal additional supplying of initial water near the wall of conical bottom (2) of housing (1) under the layer of water to be settled. Pipes (16) with openings (17) for additional discharging the clarified water are arranged under the water surface. One end of each pipe is connected with chute for the clarified water and has control valve gate (18). The other end is bent downward and has trancated cone (19) at the entrance to the pipe for the clarified water. The outlets of the pipes for discharging clarified water from the top funnel of the cyclone are provided with control gate valves (8), and outlets of the pipes are provided with hemi-cones (9) for zonal distribution of the initial water and reducing the velocity of rising water flow.

EFFECT: enhanced efficiency and reduced metal consumption for manufacturing the settler.

1 cl, 7 dwg

FIELD: physics; medicine; methods of production of production the activated water with the preset degree of variation of the water physical properties.

SUBSTANCE: the invention is pertaining to physics, medicine and may be used for production the activated water with the preset degree of variation of the water physical properties. The method consists that two connected by the tube vessels with the electrodes occupying the whole area of their bottoms are filled with the continuum volume of the distilled water. In the highest point of the tube located in the form of the arc, the water is introduced with the indicator substance representing the suspension of the pasteurized E.Coli M 17, colored with the methylene cyan, so that it has taken the form of a ball with the diameter of 0.5-0.7 cm, they feed the direct electric current on to the electrodes. At that they judge the degree of activation of the water in compliance with the time of relocation of the front of the indicating substance to the electrode, where the time interval from the beginning of the direct current feeding to the electrodes up to the moment as the front of the indicating substance will reach the near electrodes space and its direction will start to change for the opposite direction. This time interval is the time of the complete electrically activation of the water. The technical result of the invention is production of the batched electrically activated water with the preset degree of the change of its physical properties.

EFFECT: the invention ensures production of the batched electrically activated water with the preset degree of the change of its physical properties.

1 dwg, 1 tbl, 1 ex

FIELD: municipal services; methods for degassing the hot water.

SUBSTANCE: the invention is pertaining to the method of treatment of the hot water for the purpose of the water degassing before its feeding to the customers. The device for degassing the hot water, contains: the cylindrical body with the fitting pipe of water delivery for the degassing, the fitting pipe for withdrawal of the air-steam mixture, the fitting pipe for feeding of the degasified water to the customers, the pipes of the water delivery for degassing, the filling, the sprayer, the water level control in the column, the vented steam intake, the vented steam cooler, the air-steam mixture suction system. The sprayer is made out of the handedly connected to each other drained planes overlapping the whole cross section of the column above the filling. At that the axes of the hinges are collinear to the longitudinal axes of the pipes feeding the water to the degassing, and each separate plane consists of the load-bearing framework made in the form of the trapezium, between the sides of which there are the rigidly fixed on the framework rods being in parallel to the base of the trapezium and between the bases of the trapezium tipping over with respect to the rods there are the fixed metallic strips, which ends are rigidly fixed on the bases of the trapezium. At that the strips are in the staggered order bending round the load-bearing rods, and the intake of the vented steam, which body is poured with the filling made out of Rashig rings, has one movable drained bottom placed over Rashig rings. The device allows to upgrade effectiveness of the liquid degassing, to increase reliability and the cost-saving of its operation.

EFFECT: the invention ensures the upgrade of the liquid degassing efficiency, to increase reliability and the cost-saving of the device operation.

2 dwg

FIELD: chemical industry; installations and the methods of production of the synthesis-gas from the natural gas.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the installation and the method for simultaneous production from the natural gas of the methanol synthesis-gas, the ammoniac synthesis-gas, carbon monoxide and carbon dioxide. The installation consists of the in-series connected to each other assembly units and includes: the first reactor (A), in which at feeding of oxygen realize the transformation of the natural gas into the synthesis gas consisting of carbon monoxide, carbon dioxide, hydrogen and the steam; the second reactor (B), in which exercise the regular transformation of carbon monoxide into carbon dioxide; if necessary the compressor (C) using which the formed gases may be contracted; absorbing apparatus D, which serves for absorption of carbon dioxide and production of he mixture of monoxide with hydrogen used for synthesizing methanol; the refrigerating separator E, in which at feeding of the liquid nitrogen receive the ammoniac synthesis gas and simultaneously produces carbon monoxide, argon and methane. The invention allows to increase profitability of the installation due to production at one installation of several products.

EFFECT: the invention ensures the increased profitability of the installation due to production at one installation of several products.

15 cl, 1 dwg, 1 tbl

FIELD: power engineering, in particular, hydrogen and oxygen production system.

SUBSTANCE: hydrogen and oxygen production system has electric plasmochemical reactor made in the form of high-pressure cylinder with spherical bottoms provided at its ends, said bottoms being equipped with screens, through which superhigh-frequency radiation waveguides are inserted. Waveguides are separated from internal volume of reactor by metal diaphragms with supporting grids and are provided with nozzles for supplying of carbonic acid and water steam, and hollow perforated electrodes of different poles for producing and separating of hydrogen and oxygen, with internal volumes of said electrodes being connected with driers, molecular sieves for separation of hydrogen, oxygen and carbonic acid, output refrigerators, gas holder and receiver.

EFFECT: increased energy efficiency owing to reduced consumption of power, consumption of hydrogen from storages in gas-and-steam units of auxiliary electric stations at night time.

2 dwg

FIELD: chemical industry; devices for production of the synthesis gas.

SUBSTANCE: the invention is pertaining to the radial type device for realization of oxidation of the gaseous hydrocarbon fuels with the help of the catalytic agent and may be used for production of the synthesis gas. The radial type device for production synthesis gas contains the gas-distribution perforated tube 3 and the catalytic agent 4. The catalytic agent is made in the form of the annular heat-conducting dispensing catalytic plates and the heat-conducting separators with the grooves alternating among themselves with formation of channels for the gaseous streams running and connected among themselves. On the both sides of the separator 6 there are grooves 7 made in the form of the evolvent from the center to the periphery. The annular plates of the catalytic agent are mounted perpendicularly to the axis of the shafts of the gas-distribution perforated tube 3. Inside of the gas-distribution perforated tube 3 there is the starting system, which consists of the mixer 1 with the ignition plug 2 or the electric heating component. The invention presents the compact and effective device.

EFFECT: the invention presents the compact and effective radial type device used for realization of oxidation of the gaseous hydrocarbon fuels with the help of the catalytic agent and for production of the synthesis gas.

6 cl, 3 dwg

FIELD: hydrogen power engineering; the catalytic method of realization of the dimethyl ether steam conversion reaction.

SUBSTANCE: the invention is pertaining to the catalytic method of realization of the dimethyl ether (DME) steam conversion reaction for the purpose to produce the hydrogen-enriched gas mixture, which may be used in the hydrogen power engineering, in particular, as the fuel for feeding the fuel cells of the different designation. The invention presents the bifunctional catalyst of the dimethyl ether (DME) steam conversion containing the acidic centers for hydration of DME into the methanol, and the copper-containing centers for the steam conversion of methanol, and representing by itself the copper-ceric oxide deposited on the aluminum oxide. The invention also presents the method of production of the hydrogen-enriched gas mixture by interaction of DME and steam at the temperature of 200-400°C, pressure of 1-100 atm, molar ratio of H2О/DME equal to 2-10 at presence of the described above catalyst. The technical result of the invention is the high hydrogen efficiency, production of the hydrogen-containing gas with the low contents of carbon oxide at the ratio steam/DME equal to the stoichiometric (H2O/DME=3), that has the relevant technological value.

EFFECT: the invention ensures the high hydrogen efficiency, production of the hydrogen-containing gas with the low contents of carbon oxide at the suitable ratio steam to DME, that has the relevant technological value.

5 cl, 15 ex, 6 tbl

FIELD: chemical industry; methods of production of hydrogen and a methanol.

SUBSTANCE: the invention is pertaining to the method of production of the industrial hydrogen and methanol from the converted gas consisting mainly of CO2, H2. The method of production of hydrogen and methanol from the converted gas containing carbon oxides and hydrogen includes the synthesis of methanol. For execution of the methanol synthesis feed the converted gas with the volumetric ratio of H2-CO2/CO+CO2, equal to 2.03-5.4, which is conducted in the reactor system including the flow reactor or the cascade of the floe reactors and / or the reactor with the recycle of the gas mixture with production of methanol, the unreacted gas and the blow-down gas. At that the mixture of the unreacted and converted gases is fed for purification from carbon carbon dioxide with its extraction and batch feeding of the carbon dioxide into the converted gas delivered for the synthesis of methanol. The blow-down gases are subjected to the fine purification from the impurities with production of hydrogen. The invention allows to upgrade the method due to maximum usage of the carbon dioxide.

EFFECT: the invention ensures improvement of the method of production of hydrogen and a methanol due to maximum usage of the carbon dioxide.

2 cl, 1 dwg, 1 tbl, 5 ex

FIELD: hydrocarbon conversion processes.

SUBSTANCE: process consists in catalytic decomposition of hydrocarbon-containing gas at elevated temperature and pressure 1 to 40 atm, catalyst being reduced ferromagnetic cured product isolated by magnetic separation from ashes produced in coal combustion process at power stations. The catalytic product represents spinel-type product containing 18 to 90% iron oxides with balancing amounts of aluminum, magnesium, titanium, and silicon oxides. Prior to be used, catalyst is subjected to hydrodynamic and granulometric classification.

EFFECT: reduced total expenses due to use of substantially inexpensive catalyst capable of being repetitively used after regeneration, which does not deteriorate properties of original product.

2 cl, 6 ex

FIELD: petrochemical industry; methods of the synthesis of ammonia from the nitrogen and hydrogen mixture produced from the natural gases.

SUBSTANCE: the invention is pertaining to the field of petrochemical industry, in particular, to the method of the synthesis of ammonia from the nitrogen and hydrogen mixture produced from the natural gases. The method of the catalytic synthesis of ammonia from the mixture of nitrogen and hydrogen provides, that the natural gas together with the oxygen-enriched gas containing at least 70 % of oxygen is subjected to the autothermal reforming at temperature from 900 up to 1200°C and the pressure from 40 up to 100 bar at the presence of the catalyzer of cracking, producing the unstripped synthesis gas containing in terms of the dry state 55-75 vol.% of H2, 15-30 vol.% of C and 5-30 vol.% CO2. At that the volumetric ratio of H2: CO makes from 1.6 : 1 up to 4 : 1. The unstripped synthesis gas is removed from the furnace of the autothermal reforming, cooled and subjected to the catalytic conversion producing the converted synthesis gas containing in terms of the dry state at least 55 vol.% of H2 and no more than 8 vol.% of CO. The converted synthesis gas is subjected to the multistage treatment for extraction ofCO2, CO and CH4. At that they realize the contact of the synthesis gas with the liquid nitrogen and using at least one stage of the absorption treatment produce the mixture of nitrogen and hydrogen, which is routed to the catalytic synthesizing of ammonia. At that at least a part of the synthesized ammonia may be transformed into carbamide by interaction with carbon dioxide. The realization of the method allows to solve the problem of the ammonia synthesis efficiency.

EFFECT: the invention ensures solution of the problem of the ammonia synthesis efficiency.

8 cl, 1 ex, 2 tbl, 2 dwg

FIELD: chemical industry; methods of realization of reactions of reforming of hydrocarbons and production of the liquid heat carrier used as an indirect source of heat for realization of endothermal reactions.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular to the methods of realization of the reactions of reforming of hydrocarbons and is dealt with the method of production of the liquid heat carrier used as an indirect source of heat for realization of endothermal reactions, the products of which are completely independent on the liquid heat carrier. The method provides, that the flow containing hydrocarbons, and the gas flow containing oxygen, compressed in the appropriate way are fed into the combustion chamber, in which the hydrocarbons are burnt at presence of oxygen with production of the high-temperature liquid medium containing carbon dioxide and oxygen. In this high-temperature liquid medium and-or into the combustion chamber feed the flow containing water preferably in the form of steam. The given method allows to reduce the operational costs and the total power consumption.

EFFECT: the invention ensures reduction of the operational costs and the total power consumption.

9 cl, 2 dwg

FIELD: biotechnological methods and alternate fuels.

SUBSTANCE: invention concerns methods and means for production of hydrogen and carbon dioxide from brown algae for use under hydrogen power engineering conception using modern biotechnological techniques. Method according to invention resides in that feed biomass is provided by brown algae, which are gathered in Sargasso sea with the aid of trawler collectors and supplied to mother ship. At the latter, algae are processed into methane with the aid of biological enzymes and then methane undergoes steam-oxygen conversion to form synthesis gas consisting of hydrogen/carbon monoxide mixture, after which carbon monoxide is subjected to steam-assisted conversion. Resulting mixture is separated unto hydrogen and carbon dioxide. Hydrogen is purified on palladium membrane and passed to modular system of metal hydride hydrogen accumulators, while carbon monoxide is collected in gas-cylinders in compressed of liquid state. Thus obtained products are transported to sea ports in metal hydride containers and gas cylinders. Production of electric power for industrial processes is performed using fuel cell technology.

EFFECT: increased production of hydrogen and carbon dioxide from world ocean resources.

2 cl, 1 dwg

FIELD: alternate fuels.

SUBSTANCE: invention relates to a method for production of hydrogen via steam conversion of carbon monoxide and to relevant catalysts and can find used in different fields of national economy. Catalyst phase of copper-zinc-zirconium hydroxocarbonate of general formula (CuxZryZn1-x-2y)(CO3)2(OH)6 with hydrozinkite and/or aurichalcite structure, or of general formula (CuxZryZn1-x-2y)(CO3) (OH)2 with roasite structure, or containing heat treatment product thereof with general formula CuxZryZn1-x-2yO with vurcite structure, where x is number not higher than 0.7 and y number from 0.01 to 0.33. Also, method of conversion of O and H2O-containing gas mixture involving passage of reaction mixture through aforesaid catalyst bed at 150-400°C.

EFFECT: enabled preparation of heat-resistant catalyst efficiently functioning within temperature range 150 to 400°C.

4 cl, 3 dwg, 1 tbl, 7 ex

FIELD: petroleum processing catalysts.

SUBSTANCE: catalyst designed for using in petroleum fraction hydrofining, which contains oxides of cobalt, molybdenum, phosphorus, lanthanum, boron, and aluminum, is prepared by mixing aluminum hydroxide with boric acid solution and nitric acid solution of lanthanum carbonate followed by drying, calcination, impregnation of resulting carrier with cobalt nitrate and ammonium paramolybdate solution in nitric acid at pH 2.0-3.5 and 40-80°C in presence of phosphoric acid followed by drying and calcination at elevated temperature.

EFFECT: enabled production of hydrogenate with reduced content of sulfur compounds.

2 ex

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