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

FIELD: catalyst preparation methods.

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

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

7 cl, 68 ex

 

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 glavnih 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 a 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, methods of obtaining 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.

<> Thus, the known dispersion grade material Degussa P 25 firm 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. - C): 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 relatively high values of the quantum of the o outputs of 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 P 25 has an 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, recombination of the formed hydrogen atoms 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 P 25, the well-known (see, for example, inorganic synthesis Manual. 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 tetrault is xida 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 P 25 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, moreover, as a sorbent-catalyst heterogeneous photochemical oxidation of the organic 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.lnt. Ed.Engl., 1995, V.34, №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 chosen 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.lnt. Ed.Engl., 1995, V.34, No. 1, P.2017) has an average pore diameter of about 3 nanometers and has a specific surface area of about 200 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 time slice rate is ATA - 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.lnt. Ed.Engl., 1995, V.34, №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 good uporyadochennoi the 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.lnt. 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.

PE is the first 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 obrabatyvat the Nickel salt solution, and then with a solution of alkali metal borohydride to the formation of metallic 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 allows almost complete hydrolysis of tetraethoxide titanium, to form a photocatalytic active phase of anatase and save the parameters generated mesoporous structure after practice the Cesky 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 invention is illustrated specific examples of the method of obtaining a mesoporous material based on titanium dioxide, which are identified by these methods (without repeated references to the N. the x parameters of the porous structure, the 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 (for example, tetramethyl-12-crown-4 General formula C12H24O4, dibenzo-18-crown-6 the General formula C20H24About6, 18-Coronata-2-oxa-4 General formula C12H26O4N2, 18-Coronata-1-oxa-5 the General formula C12H25O5N), containing not less than 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, for example, the complex examenregeling connection tetramethyl-12-crown-4 with ion lithium General formula [Li(C12H24O4)]Cl·3H2O, the complexes of this same examkrackers the ski connection with ion barium General formula [Ba(C 12H24O4)]Cl2·3H2O and ion cerium General formula [CE(C12H24O4)]Cl3·3H2O or complex hexaazatetracyclo connection 18-Coronata-2-oxa-4 with ion sodium General formula [Na(C12H26O4N2)]Cl·3H2O, complexes of the same hexaazatetracyclo connection with ion rubidium General formula [Rb(C12H26O4N2)]Br·3H2O magnesium ion General formula [Mg(C12H26O4N2)]SO4·3H2O and ion lanthanum General formula [La(C12H26O4N2)]Cl3·7H2O. Note that 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, which contain more than ten atoms of oxygen, 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 dioxi is and titanium 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 the nation's experiments, you can 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 (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)that ska is ivalsa on 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 cooking 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 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 a solution of a substance is a template, polucen the second mixture 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 saleabration, 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 in the weeks leading up 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 protrans the governmental 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 saloobrazovanie 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 steady tendency to decrease number of mesopores in the samples of the final product and, consequently, to an increase in the amount of micropores.

Depending on the selected methods for the removal of the template (by calcination or extraction with alcohol) of the finally formed from a mixture of reage the tov spatial patterns and methods of obtaining the material necessary quantity of photocatalytic active anatase, the 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 getimplfileline 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 method described above is ke, 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/templet carried out 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 with a specific surface area of ≥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 is ture titanium dioxide/templat she was subjected to hydrothermal treatment at a temperature of from 100° With up 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 patterns 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 the finally formed spatial article shall ucture 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 extraction 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 has been the mesoporous titanium dioxide, containing no organic template.

Mesoporous titanium dioxide obtained by varying the above 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 dobavlyali thereto 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 the photocatalytic 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 rest the rum until while 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, then placed in a glass beaker. In a beaker were added the aqueous solution of alkali metal borohydride (predominantly been used stoichiometric amount of potassium borohydride, sodium borohydride or lithium borohydride), stirring the mixture, and treated them with titanium dioxide to almost full recovery in the mesopores of Nickel ions to metallic Nickel. The rate of recovery of Nickel ions by this reducing agent is practically independent of temperature. Therefore, on the basis of convenience, the process vosstanovlenie is conducted at room temperature. The time of such processing for each specific sample of powdered titanium dioxide, adsorbirovavshyei Nickel ions was determined experimentally. Note the fact that even in the case where the processing of titanium dioxide with a solution of alkali metal borohydride, the process of recovering Nickel in the mesopores of the sorbent was not fully completed, this does not affect the characteristics of the final product as a catalyst for photochemical reactions allocation of molecular hydrogen, because the first portion of hydrogen (a strong reducing agent) fully completed the recovery process.

Titanium dioxide containing mesopores of Nickel metal was separated by filtration from the solution, washed on the filter with distilled water to neutral reaction, and then washed with ethanol. The obtained composite Nickel-semiconductor mesoporous material based on titanium dioxide were 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 chloride is th Nickel. 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 with distilled water, then 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. lit., 1948, Vol. 1. - S). Isotherms of adsorption and desorption of methyl alcohol was recorded 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, M.M. Dubinin. Physico-chemical fundamentals of sorption technology. - 2nd ed., revised and supplementary - 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 of the vacuum 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 davleniya cavity 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, corresponding to this value of strain. 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 am. In the end, the specific surface SID(m2/g) sample mesoporous material based on titanium dioxide was calculated by the formula:

SID=am·NA·Ú,

where am- calculated by the BET equation (for the initial field of adsorption isotherms of methanol) monolayer capacity of methanol, mmol/g, NA- the Avogadro constant, mmol-1that Ú - the value of landing a molecule of methanol, 0.25·10-18m2the agreement is but the General 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 there):

Dcp.=4·109Vs/SID,

where SID- 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, m2/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-ZM, using copper, filtered Nickel, radiation at a voltage of 30 kV and current of 20 mA, the cracks when shooting in low-angle oblasti,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 26=25,4° in comparison with the sample dispersed material brand Degussa P 25 firm 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 in a unit of the straps (I, Einstein/min or mol-quantum/min)was determined ferrioxalate chemical actinometer using the following dependency:

I=nFe(II)/FH2,

where nFe(II)- the number of ions of iron (II)formed by irradiation of a solution of ferrioxalate, fH2, - valued quantum yield for the formation of iron (II) for a given wavelength of radiation.

Using the obtained value of I, was calculated quantum yields fH2photocatalytic 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 astoral 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 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 is 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 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, then placed in a glass beaker. In a beaker was added 150 ml of 0.13%-aqueous solution of sodium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 SID=85 m2/, As a catalyst for photochemical reactions of hydrogen from water is about-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 examanation connection dibenzo-18-crown-6 the General formula C20H24About6as 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°and consider what inou humidity 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 temperatures up to 180°it was treated hydrothermally 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 into the water, then were placed in a glass beaker. In a beaker was added 150 ml 0,033%aqueous solution of sodium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 SID=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 C28H40About10as 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 is also water-alcohol 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 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 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 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, and then crushed in dis is erature.

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, then placed in a glass beaker. In a beaker was added 150 ml 0,098%aqueous solution of sodium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 the specific surface is S ID=70 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 5

As an organic template for the synthesis of mesoporous material based on titanium dioxide used oxazaborolidine connection 18-Coronata-2-oxa-4, the General formula12H26About4N2as 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 continued 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 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 and the solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, then placed in a glass beaker. In a beaker was added 150 ml 0,055%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3.5 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 SID=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, was dissolved in 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 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 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. Filtering was separated from the ructure 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 0,167%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, then placed in a glass beaker. In a beaker was added 150 ml 0,033%aqueous solution of lithium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 quantities 09 wt.%, had a porous structure with an average pore diameter of Dcp.=8,9 nm and a specific surface area of SID=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. Temperature is a tour 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 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, then placed in a glass beaker. In a beaker was added 150 ml 0,128%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 SID=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 complex examenregeling connection tetramethyl-12-crown-4 with potassium ion General formula [K(C12H24O4)]J·2H2O as a precursor - Tetra toxic titanium General formula (C 4H9O)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 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 57 hours. After that, the structure of the place 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, then placed in a glass beaker. In a beaker was added 150 ml 0,112%aqueous solution of sodium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained crystallizes the second 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 SID=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 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 until the image is from 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. 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 patterns filtration separated ofsuspension 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, then placed in a glass beaker. In a beaker was added 150 ml 0,183%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3.5 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator until reaching constant weight.

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 SID=71 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous mother of the l on the basis of titanium dioxide provided the quantum yield of the reaction f H2=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 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 pairs in the s 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. Titanium dioxide, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, then placed in a glass beaker. In a beaker was added 150 ml 0,054%aqueous solution of sodium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide content of the al 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 SID=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 complex examenregeling connection tetramethyl-12-crown-4 with ion sodium General formula [Na(C12H24O4)]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 to about what adowanie from 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 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 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, then placed in a glass beaker. In a beaker was added 150 ml 0,062%aqueous solution of lithium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 SID=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 rubida the General formula [Rb(C 12H24O4)]Br3H2O 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 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 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 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 liquor was placed in Wroclaw, 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 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 0,144%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, then placed in a glass beaker. In a beaker was added 150 ml 0,101%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3.5 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried the vacuum desiccator 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 pore diameter of Dcp.=12,1 nm and a specific surface area of SID=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 precur the ora. 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 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 has been 7,5 the 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 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, then placed in a glass beaker. In a beaker was added 150 ml 0,183%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 Dcp.=11,3 nm and a specific surface area of SID=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 organic is anyone a template for the synthesis of mesoporous material based on titanium dioxide used complex 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 process is and, 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, then placed in a glass beaker. In a beaker was added 150 ml 0,165%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 quantities is 1.8 wt.%, had a porous structure with an average pore diameter of Dcp.=9,1 nm and a specific surface area of SID=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 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 C is La. 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 were crushed in the disperser, and then transferred to a glass beaker. There was added 150 ml,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, then placed in a glass beaker. In a beaker was added 150 ml of 0.13%-aqueous solution of sodium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 SID=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=0,112.

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 the ion stronzi the General formula [Sr(C 12H24O4)]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. 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 and toklas, where at a temperature of 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, then placed in a glass beaker. In a beaker was added 150 ml was 0.138%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in the Aquum-desiccator 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 SID=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 [VA(C12H24O4)]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 174 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 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 the whole 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 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 and the shrinking 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, then placed in a glass beaker. In a beaker was added 150 ml 0,183%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 structure with an average pore diameter of Dcp.=10,8 nm and a specific surface area of SID=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 oxide is titanium used complex examenregeling connection tetramethyl-12-crown-4 with ion lanthanum General formula [La(C 12H24O4)]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 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 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 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 and toklas, where at a temperature of 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 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, then placed in a glass beaker. In a beaker was added 150 ml 0,147%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in the Aquum-desiccator 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 SID=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 complex examenregeling connection tetramethyl-12-crown-4 with ion cerium General formula [CE(C12H24O4)]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 precurso the and. 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 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 a muffle furnace, where the structure was caliciviral at a temperature of 500°With over 4.5 hours to remove the template. The result obtained 7 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, then placed in a glass beaker. In a beaker was added 150 ml 0,183%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 SID=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 organic the ski a 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(C 20H24O6)]Cl·2C2H5OH, 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 another glass beaker was poured 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 with uterine concrete is placed 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 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, then placed in a glass beaker. In a beaker was added 150 ml 0,070%aqueous solution of lithium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in the Aquum-desiccator 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 pore diameter of Dcp.=10,9 nm and a specific surface area of SID=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 [MA(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 BBO is or 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. 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 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. In the floor is made of 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, then placed in a glass beaker. In a beaker was added 150 ml 0,183%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 SID=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 which ensure maximum quantum yield of the reaction f H2=0,130.

Example 22

As an 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 [(C20H24O6)J·2H2Oh, 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 Nitra is and ammonium. 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 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, then placed in a glass beaker. One hundred is an added 150 ml 0,048%aqueous solution of lithium borohydride and stirring the mixture, and treated them with titanium dioxide for 3.5 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 SID=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 Stekla the hydrated glass is 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, and then crushed in dis is erature.

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 0.09%-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, then placed in a glass beaker. In a beaker was added 150 ml 0,073%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 structure with an average pore diameter of Dcp.=12,0 nm and specific S ID=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 was supported by about 10°C. After samoobrazovaniya 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 of titanium dioxide was treated with a solution of this salt for 2.5 hours. Di is xed titanium, adsorbirovavshyei from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, then placed in a glass beaker. In a beaker were added 158 ml 0,147%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 SID=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 complex examenregeling connection dibenzo-18-crown-6 with magnesium ion General formula [Mg(C20H24O6)]SO4·4H2O as a precursor - tetrabutoxide is Ethan the General formula (C 4H9O)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 in an autoclave, where at a temperature of 200°it was treated hydrothermally for 51 hours. After that, the structure of the place 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, then placed in a glass beaker. In a beaker was added 150 ml of 0.017%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator until reaching constant weight.

Thus obtained mesoporous material based on titanium dioxide contained kristallicheskoe the 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 SID=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 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 within 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 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,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, then placed in a glass beaker. In a beaker was added 150 ml of a 0.12%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 pore diameter of Dcp.=10,6 nm and a specific surface area of SID=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 strontium ion on the overall formula [Sr(C 20H24About6)]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 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 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 solution was put in the autoclave, where at a temperature of 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 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, then placed in a glass beaker. In a beaker was added 150 ml 0,055%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in the Aquum-desiccator 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 SID=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 complex examenregeling connection dibenzo-18-crown-6 with ion barium General formula [VA(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 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. the donkey, as the whole 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 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 600°C for 4 hours to remove the template. The result was obtained 7.5 g of mesop ristoro 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, then placed in a glass beaker. In a beaker was added 150 ml 0,156%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 SID=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 organic the ski a 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(C 20H24O6)]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 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 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 pomeshalis autoclave, 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 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, then placed in a glass beaker. In a beaker was added 150 ml of 0.17%-aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in the cosmology vacuum-desiccator 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 pore diameter of Dcp.=13,7 nm and a specific surface area of SID=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)]Cl3·3H2Oh, 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. 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 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 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 and the shrinking in the dispersant, then transferred to a glass beaker. There was added 150 ml of 0.07%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, then placed in a glass beaker. In a beaker was added 150 ml 0,055%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 SID=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 oxide is titanium used complex 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, then placed in a glass beaker. In a beaker was added 150 ml 0,183%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in the Aquum-desiccator 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 SID=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 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 the AK entire 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 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 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 which was smelly 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, then placed in a glass beaker. In a beaker was added 150 ml 0,183%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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.=16 nm and a specific surface area of SID=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 deoxidation used complex examenregeling connection dibenzo-30-crown-10 with ion sodium General formula [Na(C 28H40O10)]Cl·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 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 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 a auto is love, 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 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 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, then placed in a glass beaker. In a beaker was added 150 ml 0,165%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in the cosmology vacuum-desiccator 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 SID=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 complex examenregeling connection dibenzo-30-crown-10 with the ion rubidium General formula [Rb(C28H40O10)]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 that is about how the whole 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 solution was placed in an autoclave where the temperature is 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 which was smelly in the dispersant, 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, then placed in a glass beaker. In a beaker was added 150 ml 0,082%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 SID=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 oxide is titanium used complex examenregeling connection dibenzo-24-crown-8 with ion cesium General formula [Cs(C 24H32O8)]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 another glass beaker was 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 liquor which was homesale in the 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 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, then placed in a glass beaker. In a beaker was added 150 ml 0,156%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in the cosmology vacuum-desiccator 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 pore diameter of Dcp.=12,7 nm and a specific surface area of SID=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(C28H40O10)]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 precurso the and. 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 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 obtained 7 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, then placed in a glass beaker. In a beaker was added 150 ml was 0.138%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 SID=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 organic the ski a template for the synthesis of mesoporous material based on titanium dioxide used complex examenregeling connection dibenzo-30-crown-10 with the calcium ion of the General formula [CA(C 28H40About10)]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 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 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 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, then placed in a glass beaker. In a beaker was added 150 ml 0,064%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in the cosmology vacuum-desiccator 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 SID=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(C24H34O8)]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 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. The village is e as the whole 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 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 from what was alkali in the dispersant, 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, then placed in a glass beaker. In a beaker were added 158 ml 0,183%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 pore diameter of Dcp.=12,0 nm and a specific surface area of SID=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 oxide is titanium used complex examenregeling connection dibenzo-30-crown-10 with the ion barium General formula [VA(C 28H40About10)]Cl2·3H2O as a precursor - tetrapropoxide titanium General formula (C4H9O)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 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 13 days prior to the final formation of a mixture of spatial structure of titanium dioxide/organic template.

Formed structure together with the mother was rastvoronasosy in the autoclave, where at a temperature of 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 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, then placed in a glass beaker. In a beaker was added 150 ml 0,147%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in the Aquum-desiccator 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 SID=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 complex examenregeling connection dibenzo-24-crown-3 with ion lanthanum General formula [La(C24H32O8)]Cl3·3H2Oh, 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. 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 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 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 and the shrinking 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, then placed in a glass beaker. In a beaker was added 150 ml 0,183%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 SID=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 oxide is titanium used complex examenregeling connection dibenzo-24-crown-8 with ion cerium General formula [CE(C 24H32O8)]Cl3·3H2Oh, 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 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 autoclave, where at a temperature of 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 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, then placed in a glass beaker. In a beaker was added 150 ml of 0.11%-aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in the cosmology vacuum-desiccator 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 pore diameter of Dcp.=16,0 nm and a specific surface area of SID=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. 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 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, hell is orbiculare from a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, then placed in a glass beaker. In a beaker was added 150 ml 0,183%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 SID=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)]Cl3·3H2O as a precursor - tetrabutoxide titanium General formula (C4H9O sub> 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, then placed in a glass beaker. In a beaker was added 150 ml 0,183%aqueous solution of potassium borohydride and stirring the mixture,and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 SID=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)]Cr·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 184 ml of this aqueous-alcoholic solvent. At room temperature, was dissolved in it 5,232 g template. In another glass top 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 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 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 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, then placed in a glass beaker. In a beaker was added 150 ml 0,183%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 2.0 wt.%, had a porous structure with an average pore diameter of Dcp.=12,4 nm and a specific surface area of SID=100 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such compositions is hydrated Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction f H2=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. 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 PA is AMI water 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 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, then placed in a glass beaker. In a beaker was added 150 ml 0,183%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the slurry solid phase by washing the do it on the filter with distilled water, then with ethanol, and then dried in a vacuum desiccator 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 SID=105 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 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·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 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 precurso the and. 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 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 when temperature is re 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, then placed in a glass beaker. In a beaker was added 150 ml 0,165%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 SID=109 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous materials is based on titanium dioxide provided the quantum yield of the reaction f H2=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. At 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 p the Rami of water 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 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 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, then placed in a glass beaker. In a beaker were added 158 ml of 0.13%-aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed and her on the filter with distilled water, then with ethanol, and then dried in a vacuum desiccator 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.=7,9 nm and a specific surface area of SID=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 pre is the cursor. 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 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 when temperature is 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, then placed in a glass beaker. In a beaker was added 150 ml 0,183%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 SID=71 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous materials is based on titanium dioxide provided the quantum yield of the reaction f H2=0,107.

Example 49

As an organic template for the synthesis of mesoporous material based on titanium dioxide used complex hexaazatetracyclo connection 18-coronata-2-oxa-4 with the magnesium ion of the General formula [Mg(C12H26O4N2)]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. Contact the CT 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 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, then placed in a glass beaker. In a beaker was added 150 ml 0,183%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the slurry solid phase, the industry is Ali it on the filter with distilled water, then with ethanol, and then dried in a vacuum desiccator 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 SID=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)]Cl2·3H2O 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 in 25 it g Ave the cursor. 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 a muffle furnace, where the structure was caliciviral when the temperature is e 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 a solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, then placed in a glass beaker. In a beaker was added 150 ml 0,046%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 pore diameter of Dcp.=10,2 nm and a specific surface area of SID=89 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous mother of the l on the basis of titanium dioxide provided the quantum yield of the reaction f H2=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 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. Comte is t 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 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, adsorbiroval the th of solution of Nickel ions, filtering was separated from the liquid phase, washed it on the filter with distilled water, then placed in a glass beaker. In a beaker was added 150 ml 0,183%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 a specific surface area of SID=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 (C4 9O)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. 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 meso is aristovo 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, then placed in a glass beaker. In a beaker was added 150 ml was 0.138%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 SID=81 m2/, As a catalyst for photochemical reactions of hydrogen from water is about-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction f H2=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 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, 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°and the relative VL is a possibility 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 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, then placed in a glass beaker. In a beaker was added 150 ml of 0.17%-aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension TBE the blowing phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 structure with an average pore diameter of Dcp.=12,2 nm and a specific surface area of SID=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 (C4H9O)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 R who was storyli 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 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 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 is 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, then placed in a glass beaker. In a beaker was added 150 ml 0,183%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 SID=86 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from in the but-alcohol mixtures such composite Nickel-semiconductor mesoporous material based on titanium dioxide provided the quantum yield of the reaction f H2=0,122.

Example 55

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 barium General formula [VA(C12H26O4N2)]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. Comte is t 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 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, then placed in a glass beaker. In a beaker was added 150 ml was 0.138%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the slurry solid phase by washing the do it on the filter with distilled water, then with ethanol, and then dried in a vacuum desiccator 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 SID=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 another glass beaker pour 45 ml of the same solvent. At room temperature, was dissolved therein 25 g p is cursor. 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 in a muffle furnace, where the structure was caliciviral when the temperature is ur 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, then placed in a glass beaker. In a beaker was added 150 ml 0,147%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 pore diameter of Dcp.=12,8 nm and a specific surface area of SID=97 m2/, As a catalyst for the photochemical reaction of hydrogen evolution from water-alcohol mixtures such composite Nickel-semiconductor mesoporous materialy the basis of titanium dioxide provided the quantum yield of the reaction f H2=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 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. Contact the CT 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 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, then placed in a glass beaker. In a beaker was added 150 ml 0,183%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the slurry solid phase by washing the do it on the filter with distilled water, then with ethanol, and then dried in a vacuum desiccator 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 SID=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 complex hexaazatetracyclo connection dibenzo-18-coronata-1-oxa-5 with ion lithium General formula [Li(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 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 an autoclave, 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 has been 7,5 the 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, then placed in a glass beaker. In a beaker was added 150 ml 0,091%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 SID=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 organic the ski a 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(C 20H26O5N)]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 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 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 in, 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 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, then placed in a glass beaker. In a beaker was added 150 ml 0,165%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in the Aquum-desiccator 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 pore diameter of Dcp.=13,8 nm and a specific surface area of SID=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(C20H26O5N)]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 is. 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 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 has been 7,5 the 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, then placed in a glass beaker. In a beaker was added 150 ml 0,046%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 SID=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 organic the ski a template for the synthesis of mesoporous material based on titanium dioxide used complex 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 solution was placed in an autoclave,where at a temperature of 200° With her 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, then placed in a glass beaker. In a beaker were added 158 ml 0,183%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator until the achievement is of constant mass.

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 SID=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 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 p is cursor. 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 a muffle furnace, where the structure was caliciviral at a temperature of 400°C for 6 hours to remove the template. The result has been 7,5 the 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, then placed in a glass beaker. In a beaker was added 150 ml of 0.13%-aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 pore diameter of Dcp.=8.3 nm and a specific surface area of SID=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 organic is wow a 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(C 20H25O5N)]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 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 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 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 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, then placed in a glass beaker. In a beaker was added 150 ml of a 0.12%aqueous solution of sodium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in the Aquum-desiccator 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 the 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 SID=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 complex hexaazatetracyclo connection dibenzo-18-coronata-1-oxa-5 with the calcium ion of the General formula [Ca(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 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 pre is the cursor. 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 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 600°C for 4 hours to remove the template. The result has been 7,5 the 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, then placed in a glass beaker. In a beaker was added 150 ml 0,044%aqueous solution of lithium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 SID=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 organizations the definition of a 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(C 20H25O5N)]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 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 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 pomeshalis autoclave, 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 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, then placed in a glass beaker. In a beaker was added 150 ml was 0.138%aqueous solution of potassium borohydride and stirring the mixture, and treated them with titanium dioxide for 3.5 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried vacuum-desiccator 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 pore diameter of Dcp.=to 11.6 nm and a specific surface area of SID=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 closing is rare. 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 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 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 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, then placed in a glass beaker. In a beaker was added 150 ml of 0.13%-aqueous solution of sodium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 SID=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 organic the ski a template for the synthesis of mesoporous material based on titanium dioxide used complex 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 liquor was placed in Wroclaw, 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, then placed in a glass beaker. In a beaker was added 150 ml 0,126%aqueous solution of sodium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried the vacuum desiccator 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 SID=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 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 p is cursor. 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 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 m is zaporizkogo 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, then placed in a glass beaker. In a beaker was added 150 ml of 0.13%-aqueous solution of sodium borohydride and stirring the mixture, and treated them with titanium dioxide for 3 hours. Filtering was separated from the suspension of solid phase, washed it on the filter with distilled water, then ethanol, then dried in a vacuum desiccator 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 pore diameter of Dcp.=15,7 nm and a specific surface area of SID=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 are not escarpa who try 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 can be forecast and meet 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 the eaction, 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.

Mesoporous material obtained as described in example 21 method and fixed in the form of a thin layer on a glass plate, was also tested as a sorbent-catalyst heterogeneous photochemical oxidation of acetone in the gas phase. For comparison we have used does not have a porous structure of highly dispersed pyrogenic 100%anatase, embodied in the form of a layer of the same thickness on the other glass plate. Sample mass mesoporous material and sample 100%anatase, engraved on the plate were equal to 0.25 was Photocatalytic oxidation of vapors of acetone was carried out at room temperature with oxygen. A plate with a layer of mesoporous material was placed in a closed glass reactor with a volume of 275 ml In the same reactor was placed a plate with a layer of non-porous 100%-n is th anatase. Introduction in the reactors of the same initial amount of vapor of acetone (to a concentration of 5·10-3mol/l), and sampling for chromatographic determination of acetone and products of its photocatalytic oxidation was performed using the dispenser through the elastic rubber membrane, tightly embedded in the walls of the reactor. Through a glass window in the walls of the reactor plate with the samples for 60 minutes was irradiated with a mercury lamp type DRSH-1000 light λ>310 nm (light intensity - 2,7·10-6Einstein/min). Photocatalytic activity of the samples was evaluated by the degree of conversion (transformation) of acetone, %, which was calculated by the formula

K=(C1-C2)·100/C1,

where C1- initial concentration of acetone in each of the reactors (5·10-3mol/l); C2the concentration of acetone in each of the reactors at the end of the irradiation of the plates with samples.

For sample mesoporous material obtained as described in example 21 method, the value K=43%. For example non-porous 100%anatase K=17. Thus, the photocatalytic activity of the proposed mesoporous material is almost 2.5 times higher than the activity does not have a porous structure of highly dispersed pyrogenic 100%anatase. In this case, as shown by the results of chromatographies the CSO analysis, when the photocatalytic oxidation of acetone by air oxygen in the presence of the inventive sorbent-catalyst no other reaction products, in addition to carbon dioxide, were recorded.

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 the quantum yield of the reaction from 0.09 to 0.13.

2. The catalyst for photochemical reactions according to claim 1, characterized in that it further comprises lanthanum in an amount of not more 0,019 grams per gram of titanium dioxide contained in the material.

3. The method of producing catalyst for photochemical reactions according to claim 1, including an introduction to 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 remove a template that distinguishes the I, 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, in the amount of from 0.001 to 0.2 mol per one mol of the precursor to the formation of the Zola the mixture of the reactants stirred, maintaining 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 its first obrabatyvat the Nickel salt solution, and then with a solution of alkali metal borohydride to the formation of metallic 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 3, characterized in that before deleting a template product reacts and treated hydrothermally at a temperature of from 100 to 200° With and template removed from the reaction product by extraction with alcohol.

6. The method according to claim 4, characterized in that before removing the template, the reaction product is treated hydrothermally at a temperature of from 100 to 200°C.

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



 

Same patents:

FIELD: mining industry.

SUBSTANCE: perovskite concentrate, which can be used for manufacture of pigment titanium dioxide for paints, paper, enamels, and plastics, is processed as follows. 1 kg of concentrate is treated under atmosphere conditions with concentrated HCl at 90-100оС for 10 to 20 h to solubilize 75-85% of titanium, radioactive, and other acid-soluble components. Concentration of HCl is then lowered by diluting it with 1-5% HCl solution until TiO2 concentration 50-100 g/L. Thermohydrolysis of solution at 100-105оС accompanied by distilling away HCl leads to residual HCl concentration 20-100 g/L. Distilled HCl is sent to processing of perovskite concentrate. Titanium-containing precipitate is separated from mother liquor, washed first with 15-37% HCl solution and then with water to pH 3. Washed precipitate is treated with aluminum acid phosphate with pH 2-4. Aluminum acid phosphate uptake (on conversion to Al2O3) constitutes 0.5 to 5.0% content of TiO2. Treated precipitate is separated and calcined at 850-870оС to give pigment titanium dioxide. From mother liquor (after separation of Ti-containing precipitate), radioactive components are isolated by 4-6-step extraction with tributyl phosphate. Organic phase-to-water phase ratio is (1.5-2.0):1. Degree of titanium recovery is at least 98%, whiteness at least 96.5 conv. units, brightening power 1650-1800 conv. units, spreading capacity 38.0-40.0 g/m2, oil capacity 25-27 g/100 g pigment. Yield of pigment TiO2 is 95.7-98.0%. Amount of radioactive precipitate does not exceed 0.06 kg.

EFFECT: optimized perovskite concentrate processing parameters.

12 cl, 4 ex

The invention relates to the production of titanium dioxide by vapor-phase hydrolysis of titanium halide

The invention relates to new particles of titanium dioxide, having a sun-protection properties and is used in cosmetic compositions

The invention relates to a method for producing titanium dioxide by hydrolysis of solutions of alkoxides of titanium

The invention relates to a method for producing pigmentary titanium dioxide from titanium containing waste, which can be used in the manufacture of paints and as a component for creating white
The invention relates to the production of compounds of titanium, such as titanium dioxide

FIELD: organic synthesis catalysts.

SUBSTANCE: invention provides improved method for preparing catalyst for synthesis of N-methylaniline from aniline and methanol. Method comprises impregnation of alumina carrier with copper nitrate solution, to which were added nitrates of modifying metals selected from group consisting of manganese, chromium, iron, cobalt, and zinc, after which impregnated carrier is dried at temperature ensuring effective conversion of deposited nitrates into oxides of corresponding metals. When calcined, catalyst is subjected to additional impregnation with copper ammine solution, wherein Cu content (on conversion to oxide) lies within 0.6 to 7.0% based on the weight of catalyst, then dried at 100-120°C, and re-calcined at 230-250°C. After first calcination Cu content is 10.1-13% and after the second it rises by 0.6-5.0%. Lifetime of catalyst increases by a factor of 1.3 to 2.

EFFECT: increased lifetime of catalyst.

1 tbl, 12 ex

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to environmentally friendly processes for production of isoalkanes via gas-phase skeletal isomerization of linear alkanes in presence of catalyst. Invention provides catalyst for production of hexane isomers through skeletal isomerization of n-hexane, which catalyst contains sulfurized zirconium-aluminum dioxide supplemented by platinum and has concentration of Lewis acid sites on its surface 220-250 μmole/g. Catalyst is prepared by precipitation of combined zirconium-aluminum hydroxide from zirconium and aluminum nitrates followed by deposition of sulfate and calcination in air flow before further treatment with platinum salts. Hexane isomer production process in presence of above-defined cat is also described.

EFFECT: increased catalyst activity.

5 cl, 2 tbl, 6 ex

FIELD: gas treatment catalysts.

SUBSTANCE: catalyst preparation method comprises depositing initially liquid soda glass onto metallic or glass-cloth surface, after which transition metal oxide mixture is sputtered onto wet surface, said transition metal oxide mixture containing, wt %: chromium (III) oxide 18-35, manganese (IV) oxide 18-35, alumina - the rest; or cupric oxide 5-15, chromium (III) oxide 10-15, alumina - the rest; or cupric oxide 12-35 and alumina - the rest. Resulting coating is dried in air during 1 day and then molded through stepwise heat treatment to temperature 400°C, which temperature is maintained for 2-2.5 h.

EFFECT: prolonged lifetime at the same catalytic efficiency.

3 tbl

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: invention relates to catalysts for isomerization of paraffins and alkylation of unsaturated and aromatic hydrocarbons contained in hydrocarbon stock. Catalyst of invention is characterized by that it lowers content of benzene and unsaturated hydrocarbons in gasoline fractions in above isomerization and alkylation process executed in presence of methanol and catalyst based on high-silica ZSM-5-type zeolite containing: 60.0-80.0% of iron-alumino-silicate with ZSM-5-type structure and silica ratio SiO2/Al2O3 = 20-160 and ratio SiO2/Fe2O3 = 30-550; 0.1-10.0% of modifying component selected from at least one of following metal oxides: copper, zinc, nickel, gallium, lanthanum, cerium, and rhenium; 0.5-5.0% of reinforcing additive: boron oxide, phosphorus oxide, or mixture thereof; the rest being alumina. Preparation of catalyst includes following steps: hydrothermal crystallization of reaction mixture at 120-180°C during 1 to 6 days, said reaction mixture being composed of precursors of silica, alumina, iron oxide, alkali metal oxide, hexamethylenediamine, and water; conversion of thus obtained iron-alumino-silicate into H-iron-alumino-silicate; further impregnation of iron-alumino-silicate with modifying metal compound followed by drying operation for 2 to 12 h at 110°C; mixing of dried material with reinforcing additive, with binder; mechanochemical treatment on vibrating mill for 4 to 72 h; molding catalyst paste; drying it for 0.1 to 24 h at 100-110°C; and calcination at 550-600°C for 0.1 to 24 h. Lowering of content of benzene and unsaturated hydrocarbons in gasoline fractions in presence of above catalyst is achieved during isomerization and alkylation of hydrocarbon feedstock carried out at 300-500°C, volumetric feedstock supply rate 2-4 h-1, weight ratio of hydrocarbon feedstock to methanol 1:(0.1-0.3), and pressure 0.1 to 1.5 MPa. In particular, hydrocarbon feedstock utilized is fraction 35-230°C of hydrostabilized liquid products of pyrolysis.

EFFECT: facilitated reduction of benzene and unsaturated hydrocarbons in gasoline fractions and other hydrocarbon fuel mixtures.

3 cl, 1 tbl, 13 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: preparation of crusted metallic catalyst comprises: (i) applying suspension containing diluent, catalytically active metal selected from cobalt and ruthenium groups, and optionally first refractory element (atomic number at least 20) oxide onto surface of carrier particles to form wet coating and (ii) removing at least part of diluent from wet coating, said suspension containing at least 5% by weight of catalytically active metal based on the weight of calcination residue, which would result after drying and calcination of suspension. Crusted metallic catalyst itself and hydrocarbon production process are also described.

EFFECT: simplified catalyst preparation technology, improved physicochemical properties of catalyst as well as selectivity thereof, and increased productivity of hydrocarbon production process.

10 cl, 1 tbl, 3 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention is dealing with catalysts showing high catalytic stability in production of chloroform from carbon tetrachloride via catalytic dehydrochlorination reaction. Catalyst containing γ-alumina-supported platinum is characterized by that platinum in the form of particles 1 to 12 nm in size is distributed throughout the bulk of microspheric γ-alumina particles having median diameter 30 to 70 μm and pore volume 0.3 -0.6 cm3/g. Preparation of catalyst involves impregnation step accomplished via spraying γ-alumina with aqueous platinum compound solution used in amount equal to or less than alumina pore volume followed by platinum compound reduction step, wherein this compound is deposited onto γ-alumina with aqueous solution of formic acid or alkali metal formate.

EFFECT: achieved retention of high catalyst activity and selectivity over a long time period without being preliminarily activated.

9 cl, 2 tbl, 4 cl

FIELD: synthesis gas generation catalysts.

SUBSTANCE: invention provides catalyst for steam generation of synthesis gas containing 2.2-8.2% nickel oxide and 3.0-6.5% magnesium oxide deposited on heat-resistant porous metallic carrier having specific surface area 0.10-0.15 m2/g, summary pore volume 0.09-0.12 cm3/g, predominant pore radius 2-20 μm, and porosity 40-60%. Synthesis gas is obtained by steam-mediated conversion of hydrocarbons at 450-850°C.

EFFECT: increased heat conductivity of catalyst and catalytic activity.

11 cl, 1 tbl, 8 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: invention provides catalyst for hydrofining of petroleum fractions, which catalyst shows elevated strength and stability upon regeneration. This is achieved supplementing alumina-based carrier with texturing additives selected from alumina and gibbsite thermochemical activation product in amount 5 to 30 wt %. Alumina additive is used with particle size not larger than 15 μm and gibbsite thermochemical activation product with that not larger than 45 μm. As binding agent in catalyst, nitric acid is used at molar ratio to alumina (0.01-0.03):1 and/or aluminum nitrate/ aluminum metal reaction product in amounts 1 to 5% based on alumina. Prior to be impregnated, catalyst is steamed at elevated temperature and impregnation is carried out from aqueous solution of nickel-cobalt-molybdenum-containing complex at pH 1-3.

EFFECT: improved performance characteristics of catalyst.

2 cl, 3 tbl, 10 ex

FIELD: catalyst preparation methods.

SUBSTANCE: immobilized ionic liquid is prepared by anion-assisted immobilization of ionic liquid, for which purpose a carrier is treated with anion source, for instance with inorganic halide to produce ionic liquid or applying it onto carrier. Alternatively, ionic liquid may be immobilized because of cation covalently linked to carrier, e.g. through silyl groups, or incorporated into carrier via synthesis of carrier in presence of acceptable base. Immobilized ionic liquid are meant for use as catalysts, e.g. in Friedel-Krafts reaction.

EFFECT: optimized preparation procedures.

18 cl, 10 ex

FIELD: precious metal technology.

SUBSTANCE: invention relates to a method for preparation of novel platinum-containing materials, which find always increasing demand in national economy, in particular in heterogeneous catalysis. According to invention, platinum is sublimated on high-temperature glass cloth with preliminarily deposited calcium oxide layer. Thus prepared material is a composite constituted by high-temperature glass cloth with deposited calcium oxide layer bearing (Ca,Si)O2 rods on its surface, said rods having oxidized platinum on their ends and metal particles 3-20 nm in size in underlayer.

EFFECT: enabled preparation of novel platinum-containing material with platinum in finely dispersed state.

7 cl, 1 dwg, 1 tbl, 6 ex

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to environmentally friendly processes for production of isoalkanes via gas-phase skeletal isomerization of linear alkanes in presence of catalyst. Invention provides catalyst for production of hexane isomers through skeletal isomerization of n-hexane, which catalyst contains sulfurized zirconium-aluminum dioxide supplemented by platinum and has concentration of Lewis acid sites on its surface 220-250 μmole/g. Catalyst is prepared by precipitation of combined zirconium-aluminum hydroxide from zirconium and aluminum nitrates followed by deposition of sulfate and calcination in air flow before further treatment with platinum salts. Hexane isomer production process in presence of above-defined cat is also described.

EFFECT: increased catalyst activity.

5 cl, 2 tbl, 6 ex

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: process is effected in reactor containing compacted bed of supported catalyst including group VIII metal, in particular cobalt, said metal being partially present in its metallic form. Supported catalyst has, on its outside surface, catalytically active metal. Compacted bed is characterized by having hollow volume more than 50 vol % and specific surface area more than 10 cm2/cm3, which is calculated as total outside surface of particles divided by bed volume.

EFFECT: improved economical efficiency of process.

8 cl, 3 tbl, 7 ex

Up!