• 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:
    This invention relates to catalysts for photo-assisted (i.e. promoted by light) oxidation-reduction (redox) reactions. These catalysts consist of colloidal particles of a semiconductor, containing on their surface a reduction catalyst and an oxidation catalyst. …<??>In a first class of catalysts, the semiconductor has a difference of energy between the valence and and the conductor band such as to permit the hole-electron separation by absorption of visible light; this semiconductor is selected, in the case of the photodecomposition of water, from TiO2 doped with Mn, Cr or Cr and Nb; CdS doped with In or Ga; SrTiO3 doped with Cr or Mn; gallium phosphide and cadmium sulpho-selenide; in the case of other photodecomposition reactions, the semiconductor is selected from the above-mentioned compounds and CdS. …<??>In a second class of catalysts, the semiconductor has a difference of energy between the valence band and the conduction band such as not to permit the hole-electron separation by absorption of visible light; this semiconductor is selected, in the case of the photodecomposition of water, from SrTiO3 and Nb2O5; in the case of other photodecomposition reactions, the semiconductor is selected from the above-mentioned compounds and TiO2 doped with Nb.
    公开号:SU1225472A3
    申请号:SU823471851
    申请日:1982-07-19
    公开日:1986-04-15
    发明作者:Виска Марио；Скотти Карло
    申请人:Сибит С.П.А. (Фирма)；
    IPC主号:
    专利说明:

    one
    The invention relates to catholic. tori for light-activated redox reactions, in particular, photodegradation of water and decarboxylation of acetic acid
    The purpose of the invention is to increase the activity of the catalyst for carrying out, the reaction without a sensitizer due to the content in the catalyst of the carrier of a certain composition and particle size with an appropriate ratio of components
    The invention is illustrated by the following examples.
    Example 1, Preparation of a catalyst consisting of CdS doped with In, on the surface of which there is RuO and Pt, and using it in photochemical decomposition into odes,
    92.7 g of CdSO are dissolved in distilled water and 1 g of InCNOj) 5HjO is added. To the resulting solution, maintained at a constant temperature of 60 ° C, add an aqueous solution of Na ,, S, maintaining the pH at a constant level of 3, 8 by adding an aqueous solution. After the precipitate is added, an additional amount is added, bringing the pH to 6, then the product is kept for 30 minutes at 60 ° C,
    The resulting product is filtered, washed with water and then with ethanol and dried under vacuum at 40 ° C.
    A part of the obtained product was subjected to annealing in a closed tube at 400 ° C for 2 hours in the presence of sulfur in order to carry out the doping of cadmium sulfide with indium sulfide. The particle size of the obtained product is 0.1-0.4 µm, 1 g of this product is dispersed in distilled water by means of ultrasonic vibrations, and added to the dispersion. 1 ml of a solution of 0.2 g of RuCl., In 100 ml of water. In the dispersion, a chloro acid is formed.
    The resulting product is dried under vacuum (200 mm Hg) in a weak stream of air at 100 ° C overnight.
    The obtained cadmium sulfide particles, on the surface of which there is RuGj (0.1 wt.%), Are dispersed once more in water at a concentration of 500 mg (CdS 1 l).
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    A solution of finely ground platinum (with a particle size of 30 A is added to the dispersion in such an amount to obtain a Pt / CdS weight ratio of 1 / 12.5, thus absorbing platinum particles on particles of indium doped cadmium sulfide,
    Get the carrier composition, wt.%: Cadmium sulfide CdS 98.7 and sulfide indium lOjSj 1.3, The catalyst contains, wt.%: The specified carrier 92.5, RuOj 0.1 and Ft 7.4,
    Using a mixture of acetic acid and sodium acetone, the pH of the dispersion was adjusted to 4.7, then EDTA (used as a decomposing substance) was added to it at a concentration of 0.1 mol, l. The dispersion is poured into a vessel with two matte surfaces and, after mixing with Nj, it is irradiated with a 450 W xenon lamp. Infrared radiation is extracted from the spectrum emitted by a lamp using a 15 cm cell filled with water and ultraviolet radiation using a filter that transmits radiation below 400 nm. In the system thus composed, hydrogen is obtained at a rate of 70 ml / h 1 l of solution.
    Example 2. Preparation of a catalyst from TiOj doped with chromium and niobium, on the surface of which there are RuOj and platinum, using this catalyst in the photochemical decomposition of water.
    A solution of TiOSO in sulfuric acid containing 0.15 wt.% Niobium based on; on tioj. (obtained by sulfuric cooking of ilmenite) is subjected to hydrolysis by heating to 95-100 ° C and diluting with water for 20 hours in a volume of water for 80 hours of a sulfuric acid solution. The metatitric acid suspension thus obtained is filtered and washed to remove soluble impurities.
    An aqueous solution containing 0.42 g of potassium dichromate is added to an acidic solution containing 300 g of TiOj and then annealed in a laboratory furnace, where for 4 hours the temperature is raised from room temperature to 750 ° C. The resulting product, containing 0.05 wt.% Chromium, acquires a light yellow hue, since chromium ions create color centers in crystals in TiO. The elementary particles of the product have
    size 200 A. The product consisting of the indicated elementary particles and their aggregates having a size of up to 2 µm is a carrier for the RuOj and Ft redox catalyst. Get the media composition, wt.%: TiOj 99,78; chromium oxide 0.07; niobium oxide .NbjOg 0.15. The catalyst contains, wt%: the specified media 92,5; RuQj 0, t; Pt 7.4. Dislers containing 500 mg / l of the product described in the example, treated with a 0.% RuO solution in the presence of 40 mg / l Pt solution at pH 4.7, release hydrogen at a rate of 1 ml / h per 1 liter of solution in the absence of sensitizers.
    Example 3. Obtaining a catalyst from cadmium sulfoselene, having on the surface of RuOj and Pt, and its use in the photochemical decomposition of water.
    92.7 g of CdSO are dissolved in distilled water to obtain a solution with a concentration of 1.30 g / l. The solution is heated to 70 ° C. To this solution, a solution of NajS at a concentration of 75 g of NajS per liter containing metallic selenium in an amount equal to 10% by weight, calculated on Na S, is added dropwise at a rate of 100 ml every 6-7 minutes.
    The amount of NagS solution added is such that it causes the complete precipitation of ions to form CdS. . The sediment contains finely chopped shlen. Then an excess amount of a solution containing selenium is added in order to bring the pH of the solution to 6-6.5. The precipitate is cooled, filtered, washed with distilled water and dried at.
    The dried product is crushed in a mortar and subjected to annealing in a nitrogen atmosphere at 500 ° C for 30 minutes.
    The product thus obtained is a solid solution of the formula, its particle size is 0.3 µm.
    The product, once again ground in a mechanical mortar, is dispersed in water and RuClj solution is added in such
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    a quantity which is sufficient to obtain 0.1% by weight of RuOj based on cadmium sulfoselenide.
    The dispersion is evaporated to dryness at 110 ° C under reduced pressure (250 mm Hg) in a weak stream of air. Platinum is added to the resulting product in an amount of 8% by weight of the amount of cadmium sulfoselenide, similar to Example 1. The catalyst contains% by weight: 92.5; RuOj 0.1; Pt 7.4. The dispersion of the obtained product in water at a concentration of 500 mg / l is subjected to irradiation, as in example 1. Thus, 9 ml / h of hydrogen per 1 l of dispersion is obtained.
    Example 4. A sample of TiOj doped with Cd and Nb is prepared, as in example 3, except that the amount of RuO on a carrier is 0.2 wt.% Pt — 4 wt.% (Calculated on TiOj). The carrier contains, wt%: TiOj 99.78; chromium oxide. niobium oxide. Nbj Og 0.15. The catalyst contains, in May.%: The said carrier 96; RuOj 0.2, and Pt 3.8. The sample is dispersed in a solution of 6 ml of 100% acetic acid in 19 ml of water. Irradiation of the dispersion allows photochemical decarboxylation of acetic acid along with the photochemical decomposition of water and other secondary reactions, such as the complete reduction of acetic acid. The amount of gases released by the reaction, expressed in terms of the rate of release of various components (in microliters per 25 ml of solution per hour), is: CH 63; COj 24; H ,, 50; ethane - traces.
    PRI me R 5 (comparative).
    The catalyst is a niobium-doped TiO catalyst containing 4 wt.% Pt and 0.1 wt.% RuOj, prepared in a known manner. It is used as an aqueous dispersion at a concentration of 500 mg / l and at a pH of 4.7. The dispersion is exposed to the visible portion of the radiation of a 450 W xenon lamp in the absence of any sensitizer. After several hours of operation, no excretion of Hj was detected.
    Circulation 527 Lodisnoe
    权利要求:
    Claims (1)
    [1]
    THE CATALYST FOR LIGHT-ACTIVATED REDUCTIVE REDUCTION REACTIONS - photodegradation of water and decarboxylation of acetic acid containing platinum, ruthenium dioxide and a carrier that is distinctive in that, in order to increase the activity of the catalyst, it contains a promoted sulfide cadmium indium sulfide in the following ratio, May.%:
    Cadmium Sulfide 98.7
    Empirical Formula Indium Sulfide 1.3 or Cadmium Sulfoselenide
    O.O. O, 2 or titanium dioxide prokotirovan by oxides of niobium and chromium at their ratio, wt.%:
    Titanium dioxide
    Chromium oxide
    Niobium oxide next
    99.78
    0,07
    0.15 at the following content of catalyst components, May.
    Platinum 3.8
    Ruthenium dioxide 0.2
    Media 96.0 or
    Platinum 7.4
    Ruthenium dioxide 0.1
    The carrier is 92.5, while the particle size of the carrier is 0.1-2 microns.
    SU „., 1225472>
    5 1225472
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    同族专利:
    公开号 | 公开日
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    EP0070712B1|1986-06-04|
    US4623437A|1986-11-18|
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    引用文献:
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    US4484992A|1981-02-04|1984-11-27|Ciba-Geigy Corporation|Process for the production of hydrogen by means of heterogeneous photoredox catalysis|FR2565844B1|1984-06-13|1988-10-28|Centre Nat Rech Scient|NOVEL NON-NOBLE METAL MICROAGGREGATES, PROCESS FOR THEIR PREPARATION AND APPLICATION TO THE CATALYSIS OF PHOTOREDUCTION OF WATER|
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