• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A catalyst for the photodecomposition of water comprises particles of Ti02 doped with Nb, and containing on their surface RuO2. This catalyst may be used, for instance, in combination with ruthenium trisbipyridyl, methylviologen and colloidal platinum. There is also described a process for the preparation of such a catalyst.
    公开号:SU1083897A3
    申请号:SU813356805
    申请日:1981-06-29
    公开日:1984-03-30
    发明作者:Виска Марио
    申请人:Сибит С.П.А.(Фирма)；
    IPC主号:
    专利说明:

    This invention relates to catalysts for the photodegradation of water. The decomposition under irradiation with visible light is based on the formation in the aqueous solution of activated complexes of the redox system capable of reacting with a suitable catalyst with the formation of hydrogen and oxygen. A known catalyst for the photodegradation of water from aqueous solutions, methyl viologen, quinones, compounds of lead, vanadium, or iron, which is a fine platinum-group metal or its oxide Cl. A disadvantage of the known catalyst is its low activity. Closest to the proposed technical essence and the achieved effect is a catalyst for the photodegradation of water, which is a ruthenium dioxide in the powder or colloidal state of C2. The disadvantage of this catalyst is its low activity. When using ruthenium dioxide in the redox system (dispersion / composition shown in Table Ij. Table 1 RuOj 100% 50 mg / 150 ml Pt 4.5 mg / 150 ml Ruthenium trispyridyl 1- 10 mol / l Methylviologen 2-10 mol / l and when irradiated with a 250 W lamp, the rate of hydrogen evolution is only 1.33 ml / h per liter of dispersion. When irradiated with a 450 W lamp, the rate of hydrogen evolution is 2.4 ml / h per liter of dispersion. The purpose of the invention is to increase the activity of the catalyst. The goal is achieved by the fact that the catalyst for photodegradation of water containing ruthenium dioxide, additionally contains niobium oxide and titanium dioxide as a carrier for ruthenium dioxide with a particle size of titanium dioxide 50-4000 A with the following content of components,% by mass: Ruthenium dioxide 0, 1-T, O Niobium oxide 0.005 - 0.6 Titanium dioxide Else According to the invention, the catalyst activity increases, as evidenced by an increase in the rate of hydrogen evolution when photo-decomposition of water is performed under identical conditions with the prototype Experiment up to 11-45 ml / h per 1 liter of dispersion for 450 W (versus 2.4 ml / h according to the prototype). Example. It is derived from a TiOS, 04 and Fe sulfuric acid solution obtained from the sulfuric acid decomposition of ilmenite (100 g of ilmenite is treated with 164 g of diluted water to a concentration of 90%) containing 0.2 wt.% Niobium (calculated as weight to mass of TiO, source of niobium It serves as an ilmenite material. The solution is heated to 95-100 s and diluted with water at the rate of 20 parts by volume of water per 80 parts by volume of sulfuric acid solution. At the end of the hydrolysis, 100 g of metatitanic acid (calculated on TiO2 in the form of an aqueous suspension with a concentration of 250 g / l (calculated on Ti02 when mixed In addition, 200 ml of a 50% by weight solution of Nc (OH at 90 ° C) is added to 200 ml of the suspension. The suspension is kept under stirring for 2 hours at 7 ° C and 90 ° C and diluted 1: 1 after dilution with distilled water and washed to until the content in the wash water is 1 g / l. To the obtained sodium titanate dispersed in water at a concentration of 200 g / l (KaKTiOzl, add a HCl solution with a concentration of 30 wt. in such an amount that after heating to pH, with stirring, the pH again becomes equal to 3tO, l. To the suspension thus obtained, another HC1 solution is added, having a concentration of 30% by weight in such an amount that the molar ratio HCl: TiO2 is 0.9. The suspension thus obtained is then heated for 2 hours at boiling point. After the reaction has been verified, the suspension is diluted with distilled water until the concentration of Ti02 is 100 g / L. Received so. the dispersion method consists of particles of Ti02 needle-like structure of rutile, having a size in the range of 1000 to 2000 A. Then 1 ml of Rosez solution (0.2 gPHCI3HOMOO ml H2O) is added to the suspension containing 1 g of TiOj. Amount | such a result is such that 0.1% T02 is obtained. The dispersion thus obtained is homogenized in an ultrasonic bath in
    for about 1 min, and then dried under vacuum of about 300 mm Hg. during the night.
    Get the catalyst of the following composition, wt,%;
    Ruthenium dioxide 0.1 Niobium oxide 0,2
    Titanium dioxide Else The resulting catalyst is used to decompose water under the action of sunlight.
    An aqueous dispersion of finely divided Pt (with particles with a diameter of approximately 30 A) is admixed to the aqueous dispersion of the catalyst. To the dispersion obtained, ristenium trisbipyridyl chloride and methylviologen are added with constant stirring.
    The pH is adjusted to 4.7. The resulting dispersion has the following concentrations:
    Pt mg / l 40.
    TiC (Nb) Ru02, mg / l 500 Trisbipyridyl chloride
    ruthenium, mol / l1-107
    Methylviologen, mol / l 5-10
    25 ml of the dispersion are placed in a 35 ml glass flask with two flat optical windows, the contents of the flask are mixed. To remove air, the dispersion is treated with a stream of nitrogen. A 450W xenon lamp is used to illuminate the sample with visible light. Radiation generated by a lamp excludes a 15 cm thick glass filled with water and a filter that inhibits radiation with a wavelength of less than 400 mm with infrared and ultraviolet components.
    During irradiation, the dispersion is continuously mixed. The gas present in the flask is then subjected to an analisous to determine the concentrations of H and O2. It is established that the rate of hydrogen formation is 45 ml / h per 1 l of the solution, and the rate of formation of 0 is 16 ml / h per 1 l of the solution.
    The composition of the catalyst, wt.%: Ti02 99,7; , -, RuOg 0.1.
    The content of active ingredients in the dispersion is as follows, May.%:
    TiO (b, OE-) RUO /, 26.40 Pt 2.11
    Ruthenium trisbipyridyl3, 38
    Methylviology 68.11. Example 2. This example illustrates the use of the catalyst according to the previous example 1 in the system where the oxidation of EDTA (Ethylenediaminetetraacetic acid) occurs and, as a result, forms only hydrogen.
    The CPU used for this purpose is diversI-identical dispersions of Example 1, except that
    there is no EDTA concentration. 5 th mol / l.
    The dispersion is irradiated with visible light, as described in Example 1.
    The rate of hydrogen formation is 300 ml / h per liter of solution.
    The composition of the aqueous dispersion is next May.%;
    TiO, (NbO / DioG .3,1
    Pt0,2
    Ruthenium trisbipyridyl0, 4
    Methylviologen7,8
    EDTA (ethylenediaminteraacetic acid) Else
    EXAMPLE 3 To a TtOS04 solution of sulfuric acid and, obtained by sulfuric acid decomposition of ilmenite, NgZO is added in such an amount to obtain 0.4 wt.% With respect to TiO and then heated to 95-100 ° C, diluted Yut water at the rate of 20 ob.h. water 80 ob.ch. sulfuric acid solution.
    The resulting suspension is filtered and washed to remove soluble contaminants.
    To a concentrated suspension containing 1 rTiO is added a solution containing 1 mg of RoC6j Chrsschia on Pu02, and thus in the final product 0.1% by weight of B02 is obtained relative to YOG. Then the product is dried under vacuum at approximately 110 ° C overnight.
    The obtained ti02 is partially amorphous and has a microcrystalline structure. Typiy anastasis. The aggregates of primary particles are formed, the size of the aggregate is 1000-2000 A, while the primary particles are 50-150 A.
    Then a catalyst dispersion with colloidal Rt and ruthenium trisbipyridyl chloride is obtained (in the absence of methylviologic
    The concentration of the components in the dispersion is as follows:
    Pt mg / l, 40
    Ti02 (NbI KuO, mg / l 500
    Trisbipyridyl chloride -i
    rutheni, mol / l 210
    The final pH of the dispersion is 4.5.
    The dispersion is then subjected to irradiation with visible light as in Example 1.
    Installed; that even in the absence of methylviologen in the system, 2 2 are generated. The rate of hydrogen injection is 2.5 ml / h per liter of solution.
    The composition of the catalyst is as follows, wt.%: T = 99.5; NbgOjO; RuO 0,1
    The composition of the aqueous dispersion of the following wt.%:
    TiOg Ru02 74.6
    Pt.-6
    Ruthenium trisbipyridyl 19.4 II of measure 4. The catalyst dispersion described in example 3 is obtained with colloidal platinum (in the absence of ruthenium trisbipyridyl and methyl viologen. The concentration of the components of dispersion, mg / l: Pt. Ti02 (Nb) RuO 500 The irradiation is carried out using the same lamp as in Example 1, but in the absence of a filter that cuts off radiation with a wavelength below 400 mm, as a result of which the dispersion is exposed to ultraviolet rays. and o despite the absence of redox system themes based on ruthenium trisbipyridyl and methyl viologen. The rate of hydrogen evolution is 15 MP / h per 1 liter of thief. The composition of active components,%: TiOy (NbOjl RuO ;, 92.6 Pt7.4) Example 5. Similarly Example 25 of preparation 3: a catalyst is prepared containing, in wt%: TiO 98.8; b; iRuO 0.5, the aqueous dispersion of the composition given in Table 2 is prepared. Table 2
    1 G / L
    41.09
    80 mg / l 3.29
    "-four.
    1-10 mol / l 2.62 5 -KTmol / l 53.00
    Note: The pH of the dispersion is 4.7.
    The dispersion is subjected to light irradiation as in Example 1. The rate of hydrogen evolution is 25 ml / h per liter of solution.
    PRI me R 6. Prepare 5 catalysts analogously to example 3, with the ratio of components set forth in Table. 3
    Table 30
    Note. pH dispersion
    corresponds to 4.7. Dispersions are exposed to visible light as in Example 1. The observed rate of hydrogen release is given in Table. five.
    Table 5 Prepare 5 aqueous dispersions,; remaining, given in Table. 4. Table4. iOg (Nb205) Ru2 500 mg / l 26.40% mg / l 2.11% of trisbyridinidyl implants 1-10 mol / l 3.38 tilviologen 5-KG mol / l 68.11
    60 Example7. Catalyst ready-,. In t analogous to example 3, it contains 0.6 wt.% N1) 2%. The catalyst is heated for 7 hours before and kept at this temperature of 10 minutes. The size of the primary particles T | (oscillates 1500 and 4000 A. These particles are coated with futlj-g of 0.5% of the mass of catgshieator in accordance with the technology of example 1. The composition of the catalyst, wt.%: 98.9; b20gO, 6 , RuOgO, 5. 1.. Preparing an aqueous dispersion of the composition shown in Table 6. Table B
     , - Ruthenium trisbipyridyl 1 "10 mol / l2.62
    Methylviologen 5-iffmole / l53.00
    Note. pH dispersion
    is 7.
    The dispersion is subjected to irradiation, visible light, as shown in example 1.
    The rate of hydrogen evolution is 12 MP / h per 1 liter of solution,
    PRI me R 8. Similarly to the example; 3 preparing catalyst, conditioner, 10
     . 1-10 gmol / l 2.62

    5 -10 g-mol / l53.00
    25 Note. PH value
    . - ,. :. -. 4.7. .
    Dispersion is exposed to visible light. As in prim 1,; ; ,,,. ,; . . Q marked The formation of hydrogen at a rate of 10 ml / h per 1 liter of solution.
    The advantage of the invention is the ability to generate
    yes when exposed to visible light with
    35
    higher performance, more than 5 times the pr water content of known catalysts. wt.%: Ru02 0,2; 0,005; TiC rest. Then, the dispersion of the catalyst with colloidal platinum is given, as given in Table. 7. T and l and c and 7
    权利要求:
    Claims (1)
    [1]
    particles of dioxide in the next somas
    0.1 - 2.0
    0.005 - 0.6 The rest is recognized as a carrier for ruthenium dioxide with a titanium size of 50 - 4000 X holding components.
    Ruthenium dioxide Niobium oxide Titanium dioxide Priority
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    同族专利:
    公开号 | 公开日
    EP0043251B1|1984-10-03|
    US4370263A|1983-01-25|
    AU7219281A|1982-01-07|
    EP0043251A3|1982-03-24|
    AU538485B2|1984-08-16|
    DE3166454D1|1984-11-08|
    CA1150230A|1983-07-19|
    IL63186D0|1981-09-13|
    EP0043251A2|1982-01-06|
    IL63186A|1984-06-29|
    BR8104129A|1982-03-16|
    IN154163B|1984-09-29|
    引用文献:
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    US4149998A|1976-04-05|1979-04-17|Exxon Research & Engineering Co.|Supported metal interaction catalysts|IT1211079B|1981-07-20|1989-09-29|Sibit S P A Ora Tioxide Italia|CATALYSTS FOR PHOTO-ASSISTED OXIDE-REDUCTION REACTIONS.|
    US4861747A|1984-06-29|1989-08-29|Exxon Research And Engineering Company|Catalysts comprising ruthenium on titania surface modified with group VA oxide of vanadium, niobium or tantalum|
    US4711871A|1984-06-29|1987-12-08|Exxon Research And Engineering Company|Catalysts comprising ruthenium on titania surface modified with group Va oxide of vanadium, niobium or tantalum|
    JP2573511B2|1988-04-06|1997-01-22|久俊 浅岡|Composition by combination of titanium, aluminum, silicon and boron tetrahedral oxides and method for producing the same|
    JPH0553543B2|1988-10-01|1993-08-10|Doryokuro Kakunenryo|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    IT23123/80A|IT1131867B|1980-06-30|1980-06-30|CATALYST FOR THE DECOMPOSITION OF WATER BY MEANS OF SOLAR ENERGY|
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