Method of preparation of cds photocatalyst for hydrogen production and a method of producing hydrogen with its application

 

(57) Abstract:

The invention relates to a method for preparing CdS photocatalyst for hydrogen production and to a method of obtaining hydrogen from water by photochemical reaction with its use. The described method of preparation of CdS-photocatalyst (photocatalytic system) used in the photolysis of water, and a method of producing hydrogen in the presence of CdS photocatalyst. Method of preparation of CdS-photocatalyst responsible of General formula (I): m(a)/Cd[M(b)]S, includes the following stages: dissolution of Cd-containing and M-containing compounds in water in such amount, in which the molar percentage of M is in the range of 0.001-20,00; added to this solution with stirring H2S or Na2S as a reagent to precipitate Cd[M]S; washing the precipitate with water and drying the precipitate under vacuum in a nitrogen atmosphere in an incubator at 105-150 C for 1.5-3.0 hours; the doping of this sludge liquid m-containing compound in such amount, in which the mass percentage of m is in the range of 0.10-5,00. In this formula, m denotes the alloying metal element as an electron acceptor selected from the group of Ni, Pd, Fe, Ru, Co and oxidized compounds any ramotar, selected from the group including V, Cr, Al, P, As, Sb and Pb; b denotes the molar percentage of M/(M+Cd) in the range of 0.001-20,00. In accordance with another object of the present invention describes a method of producing hydrogen, in which the radiation in the visible spectrum, adjusted by the optical filter, or sunlight is treated with a suspension of the photocatalyst in water which is added is 0.05 to 1.00 mol of Na2S (as electron donor) and 0.05 to 1.00 mol of Na2SO3(as reducing agent). 2 N. and 5 C.p. f-crystals, 1 table.

The technical field to which the invention relates

The present invention in General relates to a method of making photocatalyst for hydrogen production and to a method of producing hydrogen with its application, and more specifically to a method for preparing CdS photocatalyst for use in the production of hydrogen and photochemical reactions, during which in the presence of CdS, the photocatalyst of the water effectively get the hydrogen.

Background of invention

In the chemical industry hydrogen is normally used for obtaining ammonia and methanol. In addition, hydrogen is a material that is important in the process of hydrogenation, the group of hydrogen, the desulfurization, denitration and demeterova. Another example of the use of hydrogen is the contact hydrogenation of carbon dioxide, which causes global warming. Moreover, hydrogen is considered as not polluting the environment energy source, replacing existing fossil fuel.

Known methods of producing hydrogen include the extraction of fossil fuels, such as oil, modification of natural gas, the interaction of steam with iron at high temperatures, the interaction of water with the alkaline metal, the electrolysis of water.

However, due to the necessary costs of excessive amounts of heat or electrical energy, these technologies from an economic point of view are considered unattractive. With regard to the modification of fossil fuels, the known methods have another disadvantage consisting in the formation of large quantities of by-products such as carbon dioxide. In the case of electrolysis in order to simplify the purification of hydrogen is necessary to solve problems such as short service life of the electrodes and the allocation of by-products. Thus, because of the mentioned problems is the cost of the technical equipment for the PA exists in the form of various compounds, in particular in inorganic forms, but most of it is contained in water. Due to the low specific weight in the atmosphere is only a small amount of hydrogen. Purification of hydrogen contained in the form of inorganic materials are also associated with very large problems of a technological nature and economically inefficient.

Thus, in the near future a very large value can, apparently, be a method of obtaining hydrogen from water. A recently developed technology for producing hydrogen, in which the decomposition of water into hydrogen and oxygen used photochemical catalysts. To date, however, the technique related to photochemical catalysts hydrogen devoted very few publications. Typical examples of publications are published patent applications JP No. 62-191045 and 63-107815 filed on behalf of the Sho, and the couple filed by the authors of the present invention applications in South Korea, which are presented below.

Published patent application JP No. 62-191045 on behalf Sho relates to the production of hydrogen from aqueous solution of Na2's reaction photolysis in the presence of compounds of rare earth element. The compound of rare earth element has dostoino to JP patent No. 63-107815 on behalf Sho refers to the photolysis reaction, during which, as a photochemical catalyst for producing hydrogen from methanol solution in water use composite oxide of niobium and alkaline-earth metal. Similarly, the advantage of this photochemical catalyst is active in the visible region of the spectrum.

However, both mentioned known in the art methods inherent disadvantages, namely that the amount of generated hydrogen is only 10 ml/0.5 g/H.

In the patent application KR №95-7721 filed by the authors of the present invention, the above-described problem, it is suggested to a certain extent to allow using the proposed photocatalyst, corresponding to the following formula I:

The implementation of this technology has little impact on the environment and allows you to produce hydrogen at room temperature, but as promoters of hydrogen necessary oxygen-containing organic compounds.

In the patent application KR №95-30416 offered photocatalyst, corresponding to the following formula II:

The implementation of this technology has little impact on the environment and produces hydrogen at kooda, but it creates some problems of short-term life and stability of such a photocatalyst. For example, when the carrier of the photocatalyst is impregnated with an alkaline metal such as cesium, significantly increases the amount of hydrogen, but the stability of the catalyst is reduced.

Similarly, in the patent application KR №96-44214 offers a photocatalyst that meets the following formula III:

The implementation of such technology also has little impact on the environment. This connection is not only showing a certain degree of optical photocatalytic activity, but it is also relatively easy to obtain, and the photocatalyst has excellent stability. This connection has a longer lifetime, which depends on the electron donor and reductants, and the amount of hydrogen greater than by known techniques. In the case of alloying Pt instead of Cs stability of the catalyst is increased, but the amount of generated hydrogen from an economic point of view still remains insufficient.

In KR application No. 98-37179 offered photocatalyst, corresponding to the following formula IV:

Sushestvitelnoe the degree of optical activity in the visible region of the spectrum. This photocatalyst is much easier to prepare and causes the formation of much smaller quantities of by-products.

To resolve the above problems in the application of KR №98-37180 authors present invention offers a photocatalyst, corresponding to the following formula V:

This photocatalyst exhibits optical activity, an adjustable optical filter in the visible region of the spectrum, as well as sunlight. The amount of hydrogen is much higher, and the service life of such a catalyst is semi-infinite. The introduction of various alloying metals and promoters, and other, new methods allows this tool to overcome the limitations of the activity light sources and gives the opportunity to offer a simpler way of cooking. Similarly, the service life of the photocatalyst becomes longer, and the amount of hydrogen produced from water, is much greater than with the use of known in the art means. However, this tool shows limited activity for hydrogen only one reducing agent.

Description of the invention

Thus, the aim of the present invention is one which their cost-recovery system, which substantially improves the limited activity known in the art photocatalysts.

Another objective of the present invention is to develop a simplified method for preparation of the photocatalyst of the present invention, which has little impact on the environment.

In addition, the aim of the present invention is to provide a photocatalyst according to the present invention, which is characterized by optical activity in the visible spectrum, as well as sunlight, allowing a lot to increase the amount of hydrogen.

Another objective of the present invention is to provide such a service life of the photocatalyst of the present invention, which is semi-infinite.

The best option of carrying out the invention

The photocatalyst according to the present invention meets the following General formula VI:

in which m denotes the alloying metal element as an electron acceptor selected from the group comprising Ni, Pd, Fe, Ru, Co and oxidized compound of any of these metals; and denotes the mass percentage of m that are in INTA is t M/(M+Cd) in the range of 0.001-20,00.

The preparation method of photocatalyst of formula VI includes the following stages: dissolution of Cd-containing and M-containing compounds in water in such amount, in which the molar percentage of M is in the range of 0.001-20,00; added to this solution with stirring H2S or Na2S as a reagent to precipitate Cd[M]S; washing the precipitate with water and drying the precipitate under vacuum in a nitrogen atmosphere in a thermostat at about 105-150 C for 1.5 to 3.0 hours; the doping of this sludge liquid m-containing compound in such amount, in which the mass percentage of m is in the range of 0.10-5,00; oxidative sintering at a temperature of 300-400 C for 1-5 h and then reductive sintering at a temperature of 300-400 C for 1-5 h

Similar to previously known techniques of the authors of the present invention, hydrogen is produced by a method in which a suspension of the photocatalyst in water, in which the electron donor added Na2S and as a reducing agent was added NaH2PO2or Na2SO3handle radiation in the visible spectrum adjusted by means of an optical filter, or sunlight.

The GRF is with Ni, Pd, Fe, Ru, Co or oxidized connection of any of these metals; and denotes the mass percentage of m being in the range of 0.10-5,00. If this value is less than 0.10 wt.%, the amount of hydrogen decreases and decreases the stability of the photocatalyst. On the other hand, when this value exceeds 5.00 wt.%, the amount of hydrogen decreases and increases the cost of its receipt.

M denotes a promoter selected from the group including V, Cr, Al, P, As, Sb and Pb; b denotes the molar percentage of M/(M+Cd) in the range of 0.001-20,00. If the content of M is less than about 0.001 mol %, the photocatalyst loses activity, and if it exceeds 20,00 mol %, decreases the amount of hydrogen.

Acceptable molar ratio of Cd/S is 1:0.1 to 1:2,8, more preferably 1:0.6 to 1:1,4. In this range of molar ratios of the photocatalyst according to the invention shows an increased efficiency.

If in the preparation of the photocatalyst as the alloying element m using platinum (Pt) (comparative example), for Pt in the preferred embodiment, the processing of UV-irradiation should be carried out in a nitrogen atmosphere and l acid (H2PtCl6) and treated with UV-irradiation in nitrogen atmosphere for impregnation of the carrier in such a number, in which the value And for the case of Pt(A) is in the range of 0.10-5,00. Thus prepared the precipitate washed with water up until the pH of wash water reaches 7, then dried under vacuum at 105-130 C for 1.5-3 hours, subjected to oxidative sintering at 300-400 C for 1.0 to 5.0 hours and then reductive sintering at 300-400 C for 1,0-5,0 h

In the case of other alloying elements, in addition to Pt, the preferred preparation of the photocatalyst includes the following stages:

adding to the resulting draught Cd[M]S m-containing compounds other than platypodinae, in such quantity to reach values in the range of 0.10-5,00; slow addition with stirring for 6 or 7 drops of concentrated hydrochloric acid; the processing of prepared suspensions by ultrasound during 1,0-5,0 min; drying under vacuum at 110-130 C for 1.5 to 3.0 hours; oxidative sintering at 300-400 C for 1.0 to 5.0 hours and then reductive sintering at 300-400 C for 1,0-5,0 h

In the preparation of photocatalyst doped Pt (comparative example), the reason for drying and sintering in acilitie electron acceptor, Pt. It is well known that when Pt in H2PtCl6treated with UV-irradiation, Pt activates the surface of CdS and creates a connection with the spin-off's with the formation of PtS, resulting in the sintering process at a temperature of 300-400 C for 1.0 to 5.0 hours in oxidizing and reducing conditions, a structure is formed wurtzite, Pt as the electron acceptor can go to the free state of Pt(0). In a more preferred embodiment, this material should sintering at a temperature of 320-390 With, and outside of this temperature interval lifespan and optical activity of the photocatalyst decreases.

Examples of Cd-containing compounds include CdCl2, CdBr2, CdI2Cd(CH3CO2)2H2O, CdSO4H2O and Cd(NO3)24H2O, and examples of M-containing compounds include2CR2O7, CR(NO3)3, Al(NO3)3, ll3H3RHO2, NaH2PO2, As2O5, Sbl3, Pb(NO3)2, Pb(CH3CO2)4, VCl3, VOSO4, VOCl3. Examples of m-containing compounds include FeCl3, RuCl3With(NO3)2, CoCl2With(CH3CO2)2, With NISO4, Ni(NO3 is the KR patent No. 96-44214, submitted by authors of the present invention, after the primary sintering require acid etching, but the present invention is only required stage of drying the precipitate under vacuum in a nitrogen atmosphere, and thus to be excluded stage of primary sintering and etching acid.

However, in accordance with the present invention, hydrogen is produced by the dissolution of 0.15 to 1.00 mole of Na2S as an electron donor and 0.15 to 1.00 mol H2RHO2or SO2-3as the reducing agent in the primary and/or secondary distilled water or pre-treated water and added to a solution of the photocatalyst according to the present invention. Next, the thus prepared suspension is treated with irradiation in the visible region of the spectrum, an adjustable optical filter, or sunlight with stirring at a temperature of 5-85 C and under a pressure of 0.1-5 at achieving a high degree of efficiency of hydrogen.

Moreover, an important task is to maintain the concentration of electron donor and reductant in the above-mentioned limits. When it is below the lower limit, the amount of hydrogen decreases; when it is excessive, dopolnitelnuyu 10-60 C and pressures from vacuum up to 2 at.

If in the reaction environment to re-add the electron donor and the reducing agent, the service life of the photocatalyst according to the present invention becomes semi-infinite. The duration of reaction is known in the art of ZnS photocatalyst is only 6-8 hours, while the reaction time of the photocatalysts of the present invention is that all of a sudden, 20-25 h, and this means that this photocatalyst is constantly maintained high level of activity.

EXAMPLES of OBTAINING I-VII

In 125 ml of water, CdSO4H2O, K2Cr2O7as a promoter and H2S as a reagent in each case in accordance with the composition specified in the table, mix up until not shown precipitate. The resulting mixture, in which the sediment is a CdCrS, mix. The precipitate is washed with water until until the pH of the wash water is less than 7. Washed thus precipitate is dried under vacuum in a nitrogen atmosphere at a temperature of 130 C for 2 h, resulting in powder form CdCrS. To the powder CdCrS add Ni(NO3)26N2To achieve a 1 wt.% Ni. Next, with stirring, carefully add 6-7 drops of concentrated hydrochloric acid with pic 2 h, finally, oxidative sintering at a temperature of 360 C for 4 h, and then spend restorative sintering at a temperature of 360 C for 4 h with getting as ready photocatalyst Ni(1 wt.%)/Cd[Cr(0,2)]s

EXAMPLE of GETTING VIII

The experiment of example I get repeated, except that the oxidative sintering is carried out at a temperature of 360 C for 2 h, and then spend restorative sintering at a temperature of 360 C for 2 h with getting as ready photocatalyst Ni(l wt.%)/ Cd[Cr(0,2)]s

An EXAMPLE of retrieving IX

The experiment of example I get repeated, except that the oxidative sintering is carried out at a temperature of 360 C for 2.5 h, and then spend restorative sintering at a temperature of 360 C for 2.5 h with getting as ready photocatalyst Ni(1 wt.%)/Cd[Cr(0,2)]s

An EXAMPLE of OBTAINING X

The experiment of example I get repeated, except that the oxidative sintering is carried out at a temperature of 360 C for 3 h, and then spend restorative sintering at a temperature of 360 C for 3 h with getting as ready photocatalyst Ni(1 wt.%)/Cd[Cr(0,2)]s

An EXAMPLE of OBTAINING XI

Exture 360 C for 3.5 h, and then spend restorative sintering at a temperature of 360 C for 3.5 h with getting as ready photocatalyst Ni(1 wt.%)/Cd[Cr(0,2)]s

EXAMPLE XII OBTAINING

The experiment of example I get repeated, except that instead of 0.2 mol % enter of 0.05 mol % SG with getting as ready photocatalyst Ni(1 wt.%)/Cd[Cr(0,05)]s

EXAMPLE XIII OBTAINING

The experiment of example I get repeated, except that instead of 0.2 mol % using 0.1 mole % SG with getting as ready photocatalyst Ni(1 wt.%)/Cd[Cr(0,1)]s

EXAMPLE XIV OBTAINING

The experiment of example I get repeated, except that instead of 0.2 mol % enter 0.5 mol % SG with getting as ready photocatalyst Ni(1 wt.%)/Cd[Cr(0,5)]s

An EXAMPLE of OBTAINING XV

The experiment of example I get repeated, except that instead of 0.2 mole percent injected with 1.0 mol % SG with getting as ready photocatalyst Ni(1 wt.%)/Cd[Cr(l,0)]s

EXAMPLE of GETTING XVI

The experiment of example I get repeated, except that instead of Ni(NO3)26H2O use RuCl33H2O entering into the sediment ptx2">The experiment of example obtaining XVI is repeated except that the recovery stage of sintering is not carried out, to obtain the as prepared photocatalyst RUO Li2(1 wt%)/Cd[Cr(0,2)]s

EXAMPLE XIX OBTAINING

The experiment of example I get repeated, except that instead of Ni(NO3)26H2O use Co(NO3)26H2O, giving a residue of 1.0 wt.% With that obtaining in the quality of the finished photocatalyst With(1 wt%)/Cd[Cr(0,2)]s

An EXAMPLE of retrieving XX

The experiment of example I get repeated, except that instead of Ni(NO3)26H2O use of Pd(NO3)2by introducing sediment to 1.0 wt.% Pd, getting as ready photocatalyst Pd(1 wt%)/Cd[Cr(0,2)]s

EXAMPLE of GETTING XXI (comparative example)

The experiment of example I get repeated, except that instead of Ni(NO3)26H2O use H2PtCl6by introducing sediment to 1.0 wt.% Pt, getting as ready photocatalyst Pt(1 wt.%)/Cd[Cr(0,2)]s

EXAMPLE of GETTING XXII (comparative example)

The experiment of example I get repeated, except that instead of Ni(NO3)2risks of UV rays, the precipitate is washed with water to achieve a pH 7, dried at 130 C for 2 h, subjected to oxidative sintering at 360 C for 4 h and reductive sintering at 360 C for 4 h with obtaining thus the quality of the finished photocatalyst Pt(1 wt.%)/Cd[Cr(0,2)]s

EXAMPLE of GETTING XXIII (comparative example)

In 125 ml of water, CdSO4H2O 5 mol.% H3PO2as a promoter and H2S as a reagent mix up until not shown precipitate. The resulting mixture, in which the sediment is a CdPS, mix. The precipitate is washed with water until until the pH of the wash water is less than 7. Washed thus precipitate is dried under vacuum in a nitrogen atmosphere at a temperature of 130 C for 2 h, resulting in powder form CdPS. The experiment of example I get repeated, except that instead of Ni(NO3)26H2O use H2PtCl6by introducing the obtained powder CdPS to 1.0 wt.% Pt, obtaining thus the quality of the finished photocatalyst Pt(1 wt.%)/Cd[P(0,2)]s

EXAMPLE of GETTING XXIV (comparative example)

The experiment of example XXII obtaining repeated, except that instead of K2CR2ABOUT7as the promoter of EP OBTAIN XXV

The experiment of example XXIII obtaining repeated, except that instead of H2PtCl6use Ni(NO3)26N2O, introducing into the resulting powder was 1.0 wt.% Ni, getting as ready photocatalyst Ni(1 wt.%)/Cd[P(5,0)]s

EXAMPLE XXVI OBTAINING

The experiment of example I get repeated, except that instead of K2CR2ABOUT7as the promoter used Al(NO3)3with getting as ready photocatalyst Ni(1 wt.%)/Cd[Al(0,5)]s

EXAMPLE XXVII OBTAINING

The experiment of example I get repeated, except that instead of K2CR2ABOUT7as the promoter used As2O5H2O with getting as ready photocatalyst Ni(1 wt.%)/Cd[As(0,5)]s

EXAMPLE XXVIII OBTAINING

The experiment of example obtaining XXVII is repeated, except that instead of 0.5 mol % as the promoter is administered to 2.0 mol % As to produce in the quality of the finished photocatalyst Ni(1 wt.%)/Cd[As(2,0)]s

EXAMPLE of GETTING XXIX (comparative example)

The experiment of example I get repeated, except that instead of K2CR2ABOUT7as the promoter used MnCl3obtaining VH">The experiment of example obtaining XXIX is repeated except that instead of 0.2 mol % as a promoter injected 0.5 mol % MP with getting as ready photocatalyst Ni(1 wt.%)/Cd[Mn(0,5)]s

EXAMPLE XXXI OBTAINING

The experiment of example I get repeated, except that instead of K2CR2ABOUT7as a promoter use SbCl3with getting as ready photocatalyst Ni(1 wt.%)/Cd[Sb(0,5)]s

EXAMPLE XXXII OBTAINING

The experiment of example XXXI obtaining repeated, except that instead of 0.2 mol % as the promoter is administered to 2.0 mol % Sb with getting as ready photocatalyst Ni(1 wt.%)/Cd[Sb(2,0)]s

EXAMPLE XXXIII OBTAINING

The experiment of example I get repeated, except that instead of 0.01 mol % Pb as a promoter enter 0.01 mol % Pb with getting as ready photocatalyst Ni(1 wt.%)/Cd[Pb(0,01)] s

EXAMPLE XXXIV OBTAINING

The experiment of example I get repeated, except that instead of 0.1 mole % of Pb as a promoter impose 0.1 mol % Pb with getting as ready photocatalyst Ni(1 wt.%)/Cd[Pb(0,1)]s

EXAMPLE XXXV OBTAINING

The experiment of example I get again, C is on photocatalyst Ni(1 wt.%)/Cd[Pb(0,5)]s

EXAMPLE of GETTING XXXVI

The experiment of example I get repeated, except that instead of K2CR2ABOUT7as the promoter used VCl3with getting as ready photocatalyst Ni(1 wt.%)/Cd[V(0,5)]s

COMPARATIVE EXAMPLE I GET

The experiment of example I get repeated, except that enter 3 wt.% Ni with getting as ready photocatalyst Ni(3 wt%)/Cd[Cr(0,2)]s

COMPARATIVE EXAMPLE OBTAIN II

The experiment of example I get repeated, except that enter 3 wt.% Fe with getting as ready photocatalyst Fe(3 wt%)/Cd[Cr(0,2)]s

EXAMPLE I

0.5 g of photocatalyst prepared in accordance with example I get, suspended in 500 ml of water, which contains of 0.24 mol/l Na2S and 0.36 mol/l Na2SO3and prepared, the suspension is stirred at a rotation speed of the stirrer at 300 rpm in a photochemical reactor closed gascirculation system. The prepared suspension is irradiated in the visible region of the spectrum (Xe lamp of 500 watts with an optical filter that passes light with a wavelength of more than 400 nm, while the distance from the sample to the light source 4 cm) at room temperature chromatography and using the burette, reflected in the table below.

EXAMPLE II

The experiment of example I is repeated using 0.5 g of photocatalyst prepared in accordance with example obtain II, except that a molar ratio of Na2S:Na2SO3of 0.24 mol/l:0,3 b mol/l in 500 ml of water. The amount of hydrogen, which thus receive defined by gas chromatography and by using a burette, reflected in the table below.

EXAMPLE III

The experiment of example I is repeated using 0.5 g of photocatalyst prepared in accordance with example retrieve III, except that a molar ratio of N2S:PA2SO3of 0.48 mol/l:of 0.36 mol/l in 500 ml of water. The amount of hydrogen, which thus receive defined by gas chromatography and by using a burette, reflected in the table below.

EXAMPLE IV

The experiment of example I is repeated using 0.5 g of photocatalyst prepared in accordance with example receiving IV, except that a molar ratio of PA2S:PA2SO3of 0.36 mol/l:0,24 mol/l in 500 ml of water. The number of eye-catching, bodoro is given in the table below.

EXAMPLE V

The experiment of example I is repeated using 0.5 g of photocatalyst prepared in accordance with example obtain V, except that a molar ratio of Na2S:Na2SO3of 0.36 mol/l:of 0.48 mol/l in 500 ml of water. The amount of hydrogen, which thus receive defined by gas chromatography and by using a burette, reflected in the table below.

EXAMPLE VI

The experiment of example I is repeated using 0.5 g of photocatalyst prepared in accordance with example obtain VI, except that a molar ratio of Na2S:Na2SO3of 0.24 mol/l:0,24 mol/l in 500 ml of water. The amount of hydrogen, which thus receive defined by gas chromatography and by using a burette, reflected in the table below.

EXAMPLE VII

The experiment of example I is repeated using 0.5 g of photocatalyst prepared in accordance with example receiving VII, except that a molar ratio of Na2S:Na2SO3of 0.48 mol/l:of 0.48 mol/l in 500 ml of water. The amount of hydrogen, which thus receive certain WRITELINE EXAMPLES I-II

The experiment of example I is repeated using 0.5 g of photocatalyst prepared respectively in accordance with examples of the preparation VII-XXXVI and comparative examples of the preparation I and II, except that a molar ratio of Na2S:Na2SO3of 0.36 mol/l:of 0.36 mol/l in 500 ml of water. The amount of hydrogen, which thus receive defined by gas chromatography and by using a burette, reflected in the table below.

EXAMPLE XXXVII

In this experiment, to determine the lifetime of the photocatalyst prepared in accordance with example receipt II. 0.5 g of photocatalyst prepared in accordance with example obtain II, suspended in 500 ml of water, which consists of 0.36 mol/l Na2S and 0.36 mol/l Na2SO3and then after each subsequent 20-hour period with a total duration of 100 hours in prepared according to the above solution further add to 0.36 mol/l Na2S and 0.36 mol/l Na2SO3and measure the amount of hydrogen. Consequently, the average amount of gas obtained in the course of conducting this experiment, 260 ml/h, which is a similar result (262 ml/h), polycentropodidae has an almost infinite life.

Industrial applicability

The data show that the corresponding table, the photocatalysts in accordance with the present invention demonstrate the presence of transition metals, a variety of types, included as a promoter according to the new way of introduction, the optimal duration of sintering to improve the efficiency of photocatalysts, the proposed new rehabilitation system with a much cheaper sulfite, improvement activity known in the art of photocatalysts, which is limited, a more simplified preparation, providing a weak impact on the environment, and a much longer service life.

In addition, when the execution of the present invention apply the best reaction conditions and the optimal ratio of the reducing agent, the amount of hydrogen generated is considerably increased.

1. Method of preparation of CdS-photocatalyst that meet the following General formula VI:

m(a)/Cd[M(b)]S, VI

where m denotes the alloying metal element as an electron acceptor selected from the group of Ni, Pd, Fe, Ru, Co and oxidized compounds of these metals, and the hereafter is PPI, including V, Cr, Al, P, As, Sb and Pb; b denotes the molar percentage of M/(M+Cd) in the range of 0.001-20,00; comprising the following stages: dissolution of Cd-containing and M-containing compounds in water in such amount, in which the molar percentage of M is in the range of 0.001-20,00; added to this solution with stirring H2S or Na2S as a reagent to precipitate Cd[M]S; washing the precipitate with water and drying the precipitate under vacuum in a nitrogen atmosphere in a thermostat at about 105-150 C for 1.5 to 3.0 hours; the doping of this sludge liquid m-containing compound in such amount, in which the mass percentage of m is in the range of 0.10-5,00; oxidative sintering at a temperature of 300-400 C for 1-5 h and then reductive sintering at a temperature of 300-400 C for 1-5 h

2. The preparation method of photocatalyst under item 1, which includes UV-irradiation or acid treatment and sonication prior to sintering.

3. The preparation method of photocatalyst under item 1, in which the M-containing compounds include K2Cr2O7, Cr(NO3)3, Al(NO3)3, AlCl3H3PO2, Pan2RHO2, As2O5, Sbl3Pd(NO3)23, RuCl3, Co(NO3)2, CoCl2With(CH3CO2)2, With NISO4, Ni(NO3)2, Ni(CH3CO2)2, NiCl2, NiBr2, NiI2Pd(NO3)2.

4. The preparation method of photocatalyst under item 1, in which the m-containing compounds include FeCl3, RuCl3, Co(NO3)2, CoCl2With(CH3CO2)2, With NISO4, Ni(NO3)2, Ni(CH3CO2)2, NiCl2, NiBr2, NiI2Pd(NO3)2.

5. The preparation method of photocatalyst under item 1, in which the Cd-containing compounds include CdCl2, CdBr2, CdI2Cd(CH3CO2)2H2Oh, CdSO4H2O and Cd(NO3)24H2O.

6. The method of producing hydrogen, which includes the processing of radiation in the visible spectrum, adjusted by the optical filter, or sunlight aqueous suspension of photocatalyst under item 1 with simultaneous stirring, in which the aqueous suspension comprises from 0.05 to 1.00 mol/l PA2SO3as a reducing agent and 0.05 to 1.00 mol/l Na2S as an electron donor.

7. The method of producing hydrogen p

 

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The invention relates to catalysts and methods of producing nitrous oxide (N2O) by oxidation of ammonia with oxygen or oxygen-containing gas

The invention relates to chemical technology, more specifically to an improved process for the preparation of the catalyst and synthesis of 1,4-butandiol from acetylene and formaldehyde

The invention relates to the production of heterogeneous catalysts for liquid-phase oxidation of sulfur compounds (sulfur dioxides, verouderde, mercaptans) and can be used for purification of gas emissions and wastewater, energy, refining, petrochemical, chemical and pulp and paper industries
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