Including cations cdznms photocatalyst for the decomposition of water, its preparation and a method of producing hydrogen with its application

 

(57) Abstract:

The invention relates to a photocatalyst for hydrogen, the method of its preparation and to a method of producing hydrogen using it. In the application described photocatalyst CdZnMS produce hydrogen from water, the method of its preparation and a method of producing hydrogen using the photocatalyst. The photocatalyst is characterized by the following General formula: m(a)/ CdxZnyMzS in which m denotes at least one alloying metal element as an electron acceptor selected from the group comprising Ni, Pt, Ru, or oxidized compound of these metals; and denotes the mass percentage of m being in the range of 0.10-5,00; M denotes a catalytic element selected from the group comprising Mo, V, Al, Cs, Ti, Mn, Fe, Pd, Pt, P, Cu, Ag, Ir, Sb, Pb, Ga and Re; z denotes M/(Cd+Zn+M) in atomic percent, in the range of 0.05-20.00, and x and y denote respectively the Cd/(Cd+Zn+M) in atomic percent and Zn(Cd+Zn+M) in atomic percent, in the range of 10.00-89,95. Photocatalysts in accordance with the present invention have the advantage of showing a high degree of photocatalytic activity, respectively photocatalysis is eat. Thus, the implementation of the present invention allows the use of radiation sources a wide range. In addition, it was found that the use of photocatalysts of the present invention allows to overcome the limitation by reducing activity during photochemical reactions and these catalysts have a much longer service life and increased performance in hydrogen. 3 S. and 7 C.p. f-crystals, 1 table.

The technical field to which the invention relates

The invention relates to a photocatalyst for hydrogen, the method of its preparation and to a method of producing hydrogen with its use, and more particularly to a photochemical reaction, during which in the presence of CdZnMS photocatalyst is proposed in accordance with the present invention, from the water effectively and successfully from the economic point of view get hydrogen.

Background of the invention

Hydrogen is normally used for obtaining ammonia and methanol and its use as an essential element in obtaining saturated compounds. In addition, it plays a major role in Hydrotreating processes, including the accession of hydrogen, desulfuri is eplane. Moreover, hydrogen is considered as a non-polluting source of energy and the replacement of existing fossil fuels.

There are many different types of known methods of producing hydrogen, which include its extraction from 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, electrolysis of water, etc.

However, due to the necessary costs of excessive amounts of heat or electrical energy, these technologies from an economic point of view, are considered to be unfavorable, as in the modification, in particular, fossil fuels as a by-product produce large quantities of carbon dioxide. In the case of electrolysis of water is required to resolve problems such as short service life of the electrodes and the selection as a by-product of oxygen. Thus, the resolution of these problems due to the huge costs of technical means upon receipt of the hydrogen still was economically inefficient.

Due to the low specific weight of hydrogen is able to easily overcome the force of gravity, and the largest by 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. Even if the purging hydrogen from a practical point of view possible, it is also economically inefficient. Thus, the development of technology for high-purity hydrogen from water is very important for solving urgent problems of creation of substitute energy sources.

Recently developed technology for producing hydrogen, in which the decomposition of water into hydrogen and oxygen used photochemical catalyst. To date, however, the technique of photochemical catalysts hydrogen devoted very few publications. Typical examples of publications are published patent applications JP 62-191045 and 63-107815 on behalf of the Sho.

In lined with the patent application JP 62-191045 on behalf Sho shown that the hydrogen is produced from an aqueous solution of Na2's reaction photolysis in the presence of compounds of rare earth element. The compound of rare earth element as a catalyst also has the advantage that exhibits optical activity with emission in the visible region of the spectrum.

In lined ski catalyst for producing hydrogen from a solution of methanol in water use composite oxide of niobium and alkaline-earth metal. Similarly, the advantage of this photochemical catalyst is optical activity with emission in the visible region of the spectrum.

However, the aforementioned known techniques inherent disadvantages, namely that the amount of hydrogen generated is small, and the performance is only 10 ml/0.5 g/H.

In applications KR 95-7721, 95-30416 and 96-44214 also speaks and offers the possibility of resolving the above problems.

In the application KR 95-7721 offered photocatalyst, corresponding to the following formula I:

Cs(a)/K4Nb6O17I

The implementation of this technology in the presence of photocatalyst of formula I has the weakest influence on the environment and allows you to produce hydrogen at room temperature. However, oxygen-containing organic compounds, which upon receipt of the hydrogen act as promoters of hydrogen, creates a barrier to re-use these reagents.

In the application KR 95-30416 offered photocatalyst, corresponding to the following formula II:

Cs(a)M(c)/S(b) II

The implementation of this technology also has little impact on the environment and allows you to produce hydrogen at room temperatureset some problems of life and stability of the photocatalyst of formula II. For example, when the carrier of the photocatalyst is impregnated with an alkaline metal, such as cesium (Cs), significantly increases the amount of hydrogen, but the stability of the catalyst is reduced.

In addition, the application KR 96-44214 described photocatalyst, corresponding to the following formula III:

Pt(a)/Zn[M(b)]S III

The implementation of this technology likewise has little impact on the environment. Despite the dependence of electron donors and reducing agents, the photocatalyst of formula III is superior to the previously mentioned known technical solution for ease of preparation, stability and durability, and optical activity at radiation in the visible region of the spectrum. But the amount of generated hydrogen is economically inefficient.

In the application KR 98-37179 offered photocatalyst, corresponding to the following formula IV:

Pt(a)/Zn[M(b)]S IV

The implementation of such technology also has little impact on the environment, and the photocatalyst of formula IV to a certain extent shows 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 LASS="ptx2">

To resolve the above problems in the application KR 98-37180 authors present invention has been proposed photocatalyst, corresponding to the following formula V:

m(A)/Cd[M(B)]S V

The photocatalyst of formula V shows optical activity in the visible region of the spectrum, an adjustable optical filter, 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, prepared according to previously known technical solution 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 in known in the art cases. However, this tool shows limited activity for hydrogen only one reducing agent.

For an economically successful resolution of the above-mentioned problems in the application KR 99-22954 authors present invention has been proposed photocatalyst responsible slevy CdS photocatalyst (photocatalytic system), its preparation and structure of a new restorative system sulfite for cost-effective hydrogen. However, from an economic point of view, the rate of hydrogen production is still unsatisfactory.

Description of the invention

Thus, the aim of the present invention is to resolve the aforementioned problems encountered in the art, and the creation of new photocatalyst hydrogen with optical activity at radiation both in the visible and UV spectral regions.

Another objective of the present invention is to provide a photocatalyst with high reducing activity in sunlight, providing a high yield of hydrogen and of infinite service life.

Another objective of the present invention is to develop a preparation method of photocatalyst with high photocatalytic activity.

The best option of carrying out the invention

The photocatalyst of the present invention is characterized by the following General formula VII:

m(a)/CdxZnyMzS VII

in which m denotes the alloying metal elements is low; and indicates the mass percentage of m being in the range of 0.10-5,00; M denotes at least one catalytic element selected from the group comprising Mo, V, Al, Ti, Cs, Mn, Fe, Pd, Pt, P, Cu, Ag, Ir, So, Pb, Ga and Re; z denotes the ratio M/(Cd+Zn+M) in atomic percent, in the range of 0.05-20.00, and x and y denote Cd/(Cd+Zn+M) in atomic percent and Zn/(Cd+Zn+M) in atomic percent, in the interval, respectively 10,00-89,95.

Preparation of photocatalyst according to the present invention is characterized by the process of alloying with the implementation of the following stages: dissolution of Cd-containing Zn-containing and M-containing compounds in water in such amount, at which the value of M in atomic percent is in the range of 0.05-20,00, a Cd/(Cd+Zn+M) in atomic percent and Zn/(Cd+Zn+M) in atomic percent are in the interval respectively 10,00-89,95; added to this solution with stirring as a reagent H2S or Na2S for deposition CdZnMS; washing the precipitate with water and vacuum drying the precipitate in a nitrogen atmosphere; 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.

Similar to previously known technology water in which the electron donor added Na2S and as a reducing agent was added NaH2PO2or NaH2PO2handle light in the visible spectrum adjusted by means of an optical filter, sunlight or UV radiation.

The present invention is described in detail below.

Acting as electron acceptor alloy metal m in the photocatalyst of the present invention is an element selected from the group comprising Ni, Pt, Ru, or their oxides, which in the preferred embodiment is used in such amount, in which the content in mass percent is in the range of 0.10-5,00. If the number of component m is, for example, less than 0.10 wt.%, the amount of hydrogen decreases and decreases the stability of the photocatalyst. On the other hand, when the number of component m exceeds 5.00 wt.%, the amount of hydrogen decreases, and the cost of its receipt from an economic point of view are ineffective.

The M values in the photocatalyst of the present invention are selected from the group comprising Mo, V, Al, Ti, Cs, Mn, Fe, Pd, Pt, P, Cu, Ag, Ir, Sb, Pb, Ga, Re, a, z denotes M/(Cd+Zn+M) and is usually loses activity. On the other hand, if the value exceeds the upper limit, the reduced amount of hydrogen.

As for the molar ratio between Cd and S and between Zn and S, in the preferred embodiment, the molar ratio between Cd and S is in the range of 1: 0.05 to 1.4 and between Zn and S in the range of 1:0.05 to about 1.4, more preferably of 1:0.3 to 1:0.7 to. 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), for Pt in the preferred embodiment, the processing of UV-irradiation should be carried out in a nitrogen atmosphere and legitamate CdZnMS sintering. In a more preferred embodiment, to draft CdZnMS add hexachloroplatinic acid (H2PtCl6) and treated with UV-irradiation in nitrogen atmosphere for impregnation of the carrier in such a number, in which the value of m(Pt) 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 105-130oC for 1.5-3 hours, subjected to oxidative sintering at 300-400oWith over 1,0-6,0 h and then vosstanovitelniy option of making photocatalyst includes stages added to the obtained precipitate CdZnMS m-containing compound, other than platinum, in such quantities, at which the value of m reaches the interval of 0.10-5,00; add with stirring for 6 or 7 drops of concentrated hydrochloric acid; processing the prepared suspensions by ultrasound during 1,0-5,0 min; drying under vacuum at 110-130oC for 1.5 to 3.0 hours; oxidative sintering at 300-400oWith over 1,0-6,0 h and then reductive sintering at 300-400oWith over 1,0-6,0 h with getting photocatalyst.

In the preparation of photocatalyst doped with platinum, the reason for drying and sintering in an oxidizing/reducing conditions after reaching a pH of 7 is to be stored in the free state electron acceptor, Pt. It is well known that when Pt in H2PtCl6treated with UV-irradiation, Pt activates the surface CdZnMS and creates a connection with the spin-off's with the formation of PtS, resulting in the sintering process at a temperature of 300-400oWith oxidising and reducing conditions formed the wurtzite structure. In the case of sintering of the product at a temperature of 300-400oWith over 1,0-6,0 h Pt as the electron acceptor can go to the free state of Pt(0). In a more preferred variant of its SL is Skye activity of the photocatalyst decreases.

Examples of Cd-containing compounds include CdCl2, CdBr2, CdI2Cd(CH3CO2)2xH2O, CdSO4xH2O and Cd(NO3)24H2O, examples of Zn-containing compounds include ZnCl2, ZnBr2, ZnI2, Zr(CH3CO2)2xH2O, ZnSO4xH2O and Zn(NO3)2xH2O, and examples of M-containing compounds include MoCl5, VCl3, VOSO4, VOCl3, Al(NO3)3, AlCl3, TiCl4, Cs2CO3, Ti[och(CH3)2]4, K2Cr2O7,

Cr(CH3CO2)3, Cr(HCO2)3, Cr(NO3)3H3PO2, Man2RHO2, SbCl3, MnCl3, MFN3, KMnO4, Pb(NO3)2, Pb(CH3CO2)4, RuCl3, FeCl3, IrCl3Pd(NO3)2N2PtCl6,

Cu(NO3)23H2O, AgNO3, Ga(NO3)3, SnCl2, ReCl3and so on

And then also examples of m-containing compounds include H2PtCl6, RuCl3, With NISO4, Ni(NO3)2, Ni(CH3CO2)2, NiCl2, NiBr2, NiI2and so on

In the application KR 96-44214 filed before the creation of the present invention, after the primary sintering Gum in a nitrogen atmosphere, thanks on the proposed method of preparation stage of primary sintering and etching acid is optional.

However, in accordance with the present invention, hydrogen is produced by dissolving 0.15 to 1.00 mol of Na2S as an electron donor and 0.15-1.00 mol SO32-instead of N2RHO2-as the reducing agent in the primary and/or secondary distilled water or pre-treated water and adding 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 UV-irradiation with stirring at a temperature of 5-85oC and under a pressure of 0.1-5 at achieving high performance in hydrogen production.

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, additional increase in the number of hydrogen can be achieved. The optimal reaction condition is the temperature of 10-60oWith pressure from the vacuum is s photocatalyst according to the present invention is semi-infinite.

Below are examples of the preparation in accordance with the invention.

THE EXAMPLE I GET

In 250 ml of water, CdSO4H2O and ZnSO47H2O, Cl5as a promoter and H2S as a reagent to achieve the same composition as indicated in the table, mix up until not shown precipitate. The resulting mixture, in which the sediment is a CdZnMoS, 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 130oC for 2 h, resulting in powder form CdZnMoS.

Ni(NO3)26N2About this powder add thus to achieve a content of Ni in the sediment 1 wt.%. Next, with stirring, carefully add 6-7 drops of concentrated hydrochloric acid, followed by treatment of the resulting product with ultrasound for 3 min, dried at a temperature of 130oC for 2 h and finally oxidizing sintering at a temperature of 380oC for 4 h and then reductive sintering at a temperature of 380oC for 4 h with getting as ready photocatalyst Ni(1 wt. %)/Cd49,70Zn49,70Mo0.6 m, to enter into the sediment to 1.0 at.% Mo, obtaining thus eventually photocatalyst Ni(1 wt.%)/Cd49,50Mo1,0S.

EXAMPLES RETRIEVE III-VII

The experiment of example I get I repeat, adding MoCl5in order to enter into the sediment of 2.0 at.% Mo, obtaining thus eventually photocatalyst Ni(1 wt.%)/Cd49,00Zn49,00Mo2,0S.

EXAMPLE OF GETTING VIII

The experiment of example I get I repeat, adding MoCl5in order to enter into the sediment to 3.0 at.% Mo, obtaining thus eventually photocatalyst Ni(1 wt.%)/Cd48,50Zn48,50Mo3,0S.

AN EXAMPLE OF RETRIEVING IX

To the powder Cd49,70Zn49,70Mo2,0S, obtained in accordance with example retrieve III, type H2PtCl6in such a quantity that the content of Pt in this powder was 1.0 wt%. The finished powder is treated with UV irradiation (mercury lamp high pressure power 450 W at a distance from the sample 4 cm) in a nitrogen atmosphere for 0.5 h, irradiated thereby precipitate is washed with wash water up until the pH of wash water reaches 7, the washed precipitate is dried at a temperature of 130oC for 2 h with subsequent oxidative sintering in air at the rate which I am as ready photocatalyst Pt(1 wt. %)/Cd49,00Zn49,00Mo2,0S.

AN EXAMPLE OF OBTAINING X

The experiment of example I get repeated, except that instead of MoCl5use VCl3and oxidative sintering is carried out at a temperature of 380oC for 4 h, thus obtaining as a result, the photocatalyst Ni(1 wt.%)/Cd49,70Zn49,70Vfor 0.6S.

AN EXAMPLE OF OBTAINING XI

The experiment of example I get repeated, except that the VCl3add thus to enter into the sediment to 1.0 at.% V and oxidative sintering is carried out at a temperature of 380oC for 4 h, thus obtaining as a result, the photocatalyst Ni(1 wt.%)/Cd49,50Zn49,50V1,0S.

EXAMPLE XII OBTAINING

The experiment of example I get repeated, except that the VCl3add thus to enter into the sediment of 2.0 at.% V, with the receipt of a photocatalyst Ni(1 wt.%)/Cd49,00Zn49,00V2,0S.

AN EXAMPLE OF OBTAINING XIII

The experiment of example I get repeated, except that the VCl3add thus to enter into the sediment of 2.0 at.% V, and oxidative sintering is carried out at a temperature of 380oC for 2 h to obtain the result of photocatalytically I repeat, except that VCl3add thus to enter into the sediment of 2.0 at.% V, and oxidative sintering is carried out at a temperature of 380oC for 4 h with the receipt of a photocatalyst Ni(1 wt.%)/CD49,00Zn49,00V2,0S.

AN EXAMPLE OF OBTAINING XV

The experiment of example I get repeated, except that the VCl3add thus to enter into the sediment of 2.0 at.% V, and oxidative sintering is carried out at a temperature of 380oC for 6 h with the receipt of a photocatalyst Ni(1 wt.%)/Cd49,00Zn49,00V2,0S.

EXAMPLE OF GETTING XVI

The experiment of example, obtaining XI is repeated, except that the VCl3add in order to enter into the sediment to 3.0 at.% V, thus obtaining as a result, the photocatalyst Ni(1 wt.%)/Cd48,50Zn48,50V3,0S.

AN EXAMPLE OF OBTAINING XVII

The experiment of example, obtaining XI is repeated, except that the VCl3add in order to enter into the sediment of 5.0 at.% V, thus obtaining as a result, the photocatalyst Ni(1 wt.%)/Cd47,50Zn47,50V5,0S.

EXAMPLE OF GETTING XVIII

The experiment of example I get repeated, except that instead of MoCl5use WITH THE CLASS="ptx2">

EXAMPLE OF GETTING XIX

The experiment of example XVIII obtaining repeated, except that(NO3)2add in order to enter into the sediment of 2.0 at.% With, thus obtaining as a result, the photocatalyst Ni(1 Wt.%)/Cd49,00Z49,00Co2,0S.

AN EXAMPLE OF RETRIEVING XX

The experiment of example obtaining XIX is repeated, except that(NO3)2add in order to enter into the sediment of 5.0 at.% With, thus obtaining as a result, the photocatalyst Ni(1 wt.%)/Cd47,50Zn47,50Co5,0S.

EXAMPLE OF GETTING XXI

The experiment of example I get repeated, except that instead of MoCl5use Al(NO3)3and the result thus obtained photocatalyst Ni(1 wt.%)/Cd49,70Zn49,70Alfor 0.6S.

EXAMPLE OF GETTING XXII

The experiment of example obtaining XIX is repeated, except that Al(NO3)3add in order to enter into the sediment of 2.0 at.% Al, thus obtaining as a result, the photocatalyst Ni(l wt.%)/Cd49,00Zn49,00Al2,0S.

EXAMPLE OF GETTING XXIII

The experiment of example obtaining XIX is repeated, except that Al(NO3)3add in order to enter into the sediment of 5.0 at.% Al, getting BR>
The experiment of example I get repeated, except that instead of MoCl5use Cs2CO3and the result thus obtained photocatalyst Ni(1 wt.%)CD49,70Zn49,70Csfor 0.6S.

EXAMPLE OF GETTING XXV

The experiment of example obtaining XXIV is repeated except that Cs2CO3add in order to enter into the sediment of 2.0 at.% Cs, thus obtaining as a result, the photocatalyst Ni(1 wt.%)/Cd49,00Zn49,00Cs2,0S.

EXAMPLE OF GETTING XXVI

The experiment of example I get repeated, except that instead of MoCl5use Ti[OCH(CH3)2] 4and the result thus obtained photocatalyst Ni(1 wt.%)/Cd49,70Zn49,70Tifor 0.6S.

EXAMPLE XXVII OBTAINING

The experiment of example XXVI obtaining repeated, except that Ti[och(CH3)2]4add in order to enter into the sediment of 2.0 at.% Ti, thus obtaining as a result, the photocatalyst Ni(1 wt.%)/Cd49,00Zn49,00Ti2,0S.

EXAMPLE XXVIII OBTAINING

The experiment of example XXVI obtaining repeated, except that Ti[OCH(CH3)2] 4add in order to enter into the sediment of 5.0 at.% Ti, so epxperience example get I repeat, except that instead of MoCl5as a promoter use MFN3and the result thus obtained photocatalyst Ni(1 wt.%)/Cd49,70Zn49,70Mnfor 0.6S.

EXAMPLE OF GETTING XXX

The experiment of example obtaining XXIX is repeated except that the MFN3as a promoter added in order to enter into the residue of 0.2 at.% Mn, thus obtaining as a result, the photocatalyst Ni(1 wt. %)/Cd49,90Zn49,90Mnof 0.2S.

EXAMPLE XXXI OBTAINING

The experiment of example I get repeated, except that instead of MoCl5as a promoter using H3PO2and the result thus obtained photocatalyst Ni(1 wt.%)/Cd47,00Zn47,00P6,0S.

EXAMPLE XXXII OBTAINING

The experiment of example obtaining III is repeated, except that instead of NiCl26H2O use RuCl33H2O in order to enter into the sediment to 1.0 wt.% EN, thus obtaining as a result, the photocatalyst EN (1 wt. %)/Cd47,00Zn47,00P6,0S.

EXAMPLE XXXIII OBTAINING

The experiment of example XXXI obtaining repeated, except that as a promoter using H3RHO2in order to enter into the sediment 10.0 wt.% R, teachings XXXIV

The experiment of example I get repeated, except that instead of MoCl5as a promoter using FeCl3and in the end you get a photocatalyst Ni(1 wt.%)/Cd49,70Zn49,70Fefor 0.6S.

EXAMPLE XXXV OBTAINING

The experiment of example I get repeated, except that instead of MoCl5as a promoter using Pd(NO3)2and in the end you get a photocatalyst Ni(1 wt.%)/Cd49,70Zn49,70Pdfor 0.6S.

EXAMPLE OF GETTING XXXVI

The experiment of example I get repeated, except that instead of MoCl5as a promoter using H2PtCl6and in the end you get a photocatalyst Ni(1 wt.%)/CD49,70Zn49,70Ptfor 0.6S.

EXAMPLE XXXVII OBTAINING

The experiment of example I get repeated, except that instead of l5as a promoter using Cu(NO3)23H2O and end up with the photocatalyst Ni(1 wt.%)/Cd49,70Zn49,70Cufor 0.6S.

EXAMPLE XXXVIII OBTAINING

The experiment of example I get repeated, except that instead of MoCl5as a promoter use AgNO3and in the end you get a photocatalyst Ni(1 wt.%)/Cd49,70Znthe group also instead MoCl5as a promoter use IrCl3and in the end you get a photocatalyst Ni(1 wt.%)/Cd49,70Zn49,70Irfor 0.6S.

AN EXAMPLE OF OBTAINING XL

The experiment of example I get repeated, except that instead of MoCl5as a promoter use Pb(NO3)2and in the end you get a photocatalyst Ni(1 wt.%)/Cd49,70Zn49,70Pbfor 0.6S.

EXAMPLE OF GETTING XLI

The experiment of example I get repeated, except that instead of MoCl5as a promoter using SnCl2and in the end you get a photocatalyst Ni(1 wt.%)/Cd49,70zn49,70Snfor 0.6S.

EXAMPLE OF GETTING XLII

The experiment of example I get repeated, except that instead of ModCl5as a promoter use Ga(NO3)3and in the end you get a photocatalyst Ni(1 wt.%)/Cd49,70Zn49,70Gafor 0.6S.

EXAMPLE OF GETTING XLIII

The experiment of example I get repeated, except that instead of MoCl5as a promoter use ReCl3and in the end you get a photocatalyst Ni(1 wt.%)/Cd49,70Zn49,70Refor 0.6S.

EXAMPLE OF GETTING XLIV

The experiment of example I get the surface is t photocatalyst Ni(1 wt.%)/Cd49,70Zn49,70Sbfor 0.6S.

EXAMPLE OF GETTING XLV

The experiment of example I get repeated, except that K2Cr2O7as a promoter added in order to enter into the residue of 0.2 at.% Cr, thus obtaining as a result, the photocatalyst Ni(1 wt. %)/Cd49,90Zn49,90Crof 0.2S.

EXAMPLE OF GETTING XLVI

The experiment of example obtaining XLV repeated, except that the type of Cd and Zn in order to enter into the sediment, respectively 39,90 at.% Cd and 59,90 at. % Zn, thus obtaining as a result, the photocatalyst Ni(1 wt. %)/Cd39,90Zn59,90Crof 0.2S.

EXAMPLE OF GETTING XLVII

The experiment of example obtaining XLV repeated, except that the type of Cd and Zn in order to enter into the sediment, respectively 59,90 at.% Cd and 39,90 at. % Zn, thus obtaining as a result, the photocatalyst Ni(1 wt. %)/Cd59,90Zn39,90Crof 0.2S.

EXAMPLE OF GETTING XLVIII

The experiment of example obtaining XLV repeated, except that K2Cr2ABOUT7as a promoter added in order to enter into the sediment of 0.5 at.% Cr, thus obtaining as a result, the photocatalyst Ni(1 wt. %)/Cd49,75Zn49,75Cr0,5S.

EXAMPLE OF GETTING XLIX

Experimentat with the to enter into the sediment to 1.0 at.% Cr, thus obtaining as a result, the photocatalyst Ni(1 wt. %)/Cd49,50Zn49,50Cr1,0S.

EXAMPLE FOR L

The experiment of example obtaining XLV again, thus obtaining as a result, the photocatalyst Ni(1 wt.%)/Cd49,90Zn49,90Crof 0.2S.

AN EXAMPLE OF RETRIEVING LI

The experiment of example of a III repeat, thus obtaining as a result, the photocatalyst Ni(1 wt.%)/Cd49,00Zn49,00Mo2,0S.

COMPARATIVE EXAMPLE I GET

The experiment of example obtaining XL repeat in order to enter 0,05 wt. % Ni, receiving as a result, the photocatalyst Ni(0,05 wt.%)/Cd49,70Zn49,70Pbfor 0.6S.

COMPARATIVE EXAMPLE OBTAIN II

The experiment of example obtaining XL repeat in order to enter to 7.0 wt.% Ni, receiving as a result, the photocatalyst Ni(7.0 wt%)/Cd49,70Zn49,70Pbfor 0.6S.

COMPARATIVE EXAMPLE RETRIEVE III

The experiment of example obtaining XLV repeat in order to enter 91,80 at.% Cd and 8.00 at.% Zn, receiving as a result, the photocatalyst Ni(1 wt. %)/Cd91,80Zn8,00Crof 0.2S.

COMPARATIVE EXAMPLE RECEIVING IV

The experiment of example obtaining XLV repeat in order to enter 8,00 at. % Cd and 91,80 at.% Zn, polucha V

The experiment of example obtaining XLVIII repeated, except that after oxidative sintering reductive sintering is conducted for 30 minutes at a temperature of 380oWith getting so eventually photocatalyst Ni(1 wt.%)/Cd49,75Zn49,75Cr0,5S.

EXAMPLES I-XLIX AND COMPARATIVE EXAMPLES I-V

0.5 g of photocatalyst prepared in accordance with each of examples obtain I-XXIII and comparative examples obtain I-V, independently suspended in 500 ml of water, which includes 0.36 M Na2S and 0.36 M 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 and under a pressure of 1 ATA. The amount of hydrogen, which thus receive defined by gas chromatography and by using a burette, indicated in the table.

EXAMPLE L

The experiment of example I is repeated, except that instead of the Xe lamp m is tragedy in the table.

EXAMPLE LI

Life photocatalyst prepared in accordance with example retrieve III, was determined as follows. 0.5 g of photocatalyst prepared in accordance with example retrieve III, suspended in 500 ml of water, which consists of 0.36 mol/l Na2S and 0.36 mol/l Na2SO3and then after each subsequent 10-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 number of gaseous hydrogen produced during the described experiment is 980 ml/h, which is a similar result (972 ml/h) obtained in example XVII. Thus, the result obtained during this experiment proves that the photocatalyst has a semi-infinite service life.

Industrial applicability

From these data it is obvious that CdZnMS photocatalyst in accordance with the present invention includes both photocatalytic CdS group, exhibiting properties of high catalytic activity upon irradiation in the visible region of the spectrum, the development of UV-irradiation, what makes such a photocatalyst can be used in combination with radiation sources of a wider range than previously known photocatalysts.

In addition, the implementation of the present invention by implementing the following techniques, such as adding other new alloying metals and various promoters, development of new ways of introducing and defining the optimal duration of sintering, eliminates difficulties associated with pre-existing restrictions on the activity of photocatalysts in relation to entering the reaction of the reducing agent.

Moreover, thanks to the optimal composition of Cd/Zn and the reaction conditions, these photocatalysts are also excellent predictable durability as well as performance in hydrogen.

The invention and its advantages can easily be understood from the above description. It is obvious that the proposed methods and compositions can be made a variety of changes, without exceeding the essence and scope of the invention or without sacrificing its material advantages. These methods and compositions in the present description are presented simply to illustrate prefer etousa the formula:

m(a)/CdxZnyMzS,

in which m denotes the alloying metal element as an electron acceptor selected from the group comprising Ni, Pt, Ru, or oxides of any of these metals;

and indicates the mass percentage of m being in the range of 0.10-5,00;

M denotes a catalytic element selected from the group comprising Mo, V, Al, Cs, Ti, Mn, Fe, Pd, Pt, P, Cu, Ag, Ir, Sb, Pb, Ga and Re;

x refers to the ratio of Cd/(Cd+Zn+M) in atomic percent, in the range of 10.00-89,95;

y denotes the ratio of Zn/(Cd+Zn+M) in atomic percent, in the range of 10.00-89,95;

z denotes M/(Cd+Zn+M) in atomic percent, in the range of 0.05-20,00 respectively.

2. The preparation method of photocatalyst CdZnMS under item 1, which includes stages of dissolution of Cd-containing Zn-containing and M-containing compounds in water in such amount, in which M/(Cd+Zn+M) in atomic percent is in the range of 0.05-20.00, and Cd/(Cd+Zn+M) in atomic percent and Zn/(Cd+Zn+M) in atomic percent are in the interval respectively 10,00-89,95, added to this solution with stirring as a reagent N2S or Na2S for deposition of CdxZnyMzS, washing the precipitate with water and vacuum suscha thus precipitate by adding thereto liquid m-containing compound in the amount of 0.10-5.00 wt.%.

3. The preparation method of photocatalyst CdZnMS under item 2, in which the alloying process includes sintering after UV-irradiation or acid treatment and ultrasonic treatment.

4. The preparation method of photocatalyst CdZnMS under item 2, in which the M-containing compound is a member selected from the group comprising l5, VCl3, VOSO4, VOCl3, Al(NO3)3, AlCl3, TiCl4Cs2CO3, Ti[OCH(CH3)2]4, K2Cr2O7, Cr(CH3CO2)3, Cr(HCO2)3, Cr(NO3)3H3PO2, NaH2PO2,

SbCl3, MnCl3, MFN3, KMnO4, Pb(NO3)2, Pb(CH3CO2)4, RuCl3, FeCl3, IrCl3,

Pb(NO3)2H2PtCl6, Cu(NO3)23H2O, AgNO3, Ga(NO3)3, SnCl2and ReCl3. 5. The preparation method of photocatalyst CdZnMS under item 2, in which the m - containing compound is a member selected from the group comprising H2PtCl6, RuCl3, With NISO4, Ni(NO3)2, Ni(CH3CO2)2, NiCl2, NiBr2and Nil2.

6. The preparation method of photocatalyst CdZnMS under item 2, wherein, when the temperature in the range of 300-400oAfter UV-irradiation in nitrogen atmosphere.

7. The preparation method of photocatalyst CdZnMS under item 2, in which the Cd-containing compound is a member selected from the group comprising CdCl2, CdBr2, CdI2Cd(CH3CO2)2xH2O, CdSO4xH2On Cd(NO3)24H2Oh, and Zn - containing compound is a member selected from the group comprising ZnC12, ZnBr2, ZnI2, Zn(CH3CO2)2xH2O, ZnSO4xH2O and Zn(NO3)2xH2O. 8. The preparation method of photocatalyst CdZnMS under item 2, which, when m does not denote platinum, includes front vacuum drying treatment with hydrochloric acid and ultrasound.

9. The method of producing hydrogen using the photocatalyst CdZnMS, which differs in that it includes a stage of processing aqueous suspension of photocatalyst under item 1, which comprises 0.05 to 1.00 mol/l Na2S as an electron donor and 0.05 to 1.00 mol/l Na2SO3as reducing agent, radiation in the visible spectrum, adjusted by the optical filter, or UV-irradiation with simultaneous stirring.

10. The method of producing hydrogen using the photocatalyst CdZnMS under item 9, Kuuma up to 2 ATA.

 

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