Product intended to be used as a photocatalyst, method for the preparation of such product and utilization of such product

• US 4,427,749 A
• Filed: 01/27/1982
• Issued: 01/24/1984
• Est. Priority Date: 02/02/1981
• Status: Expired due to Term

• Current Assignee: Eniricerche S.P.A.
• Original Assignee: Michael Graetzel
• Inventors: Duonghong, Dung, Graetzel, Michael, Borgarello, Enrico, Kalyanasundaram, Kuppuswamy, Neumann-Spallart, Michael
• Primary Examiner(s): Weisstuch, Aaron
• Application Number:
  US06/343,177
• Time in Patent Office: 727 Days
• Field of Search: 204/72, 204/75, 204/77, 204/114, 204/128, 204/129, 204/290 R, 204/290 F, 204/242, 204/257, 204/278, 204/DIG. 3, 429/111, 427/74
• US Class Current: 429/111
• CPC Class Codes: C25B 1/55 Photoelectrolysis
• CPC Class Codes: H01G 9/20 Light-sensitive devices
• CPC Class Codes: H01M 14/005 Photoelectrochemical storage cells light sensitive devices H01G9/20, semiconductors sensitive to light H01L31/00
• CPC Class Codes: Y02E 10/542 Dye sensitized solar cells
• CPC Class Codes: Y02E 60/36 Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
• CPC Class Codes: Y02P 20/133 Renewable energy sources, e.g. sunlight
• CPC Class Codes: Y10S 204/03 Auxiliary internally generated electrical energy

Abstract

The product is in the form of discrete particles or in the form of a layer comprising an electrode. It consists of a semi-conductor material subject to photo-corrosion, for example, cadmium sulphide. In order to prevent such photo-corrosion, the surface of the semi-conductor material, which is intended to be illuminated, is covered with a transparent layer of RuO₂, IrO₂ or a mixture of RuO₂ and IrO₂.

The product may be used for the conversion of solar energy into electric energy or into a fuel such as hydrogen.

Claims

1. Product usable as a photocatalyst, comprising a semi-conductor material in the form of discrete particles or as a layer which comprises part of an electrode, said semi-conductor material being subject to photo-corrosion, characterized in that the surface of the semi-conductor material which is intended to be illuminated is covered with a transparent layer of ruthenium oxide (RuO₂), iridium oxide (IrO₂), or a mixture of ruthenium oxide (RuO₂) and iridium oxide (IrO₂), which inhibits the photo-corrosion of the semi-conductor material.

2. Product according to claim 1, characterized in that the semi-conductor material is a material selected from cadmium sulphide (CdS), cadmium selenide (CdS), gallium phosphide (GaP) and silicon (Si).

3. Product according to any one of claims 1 and 2, in the form of discrete particles, characterized in that one surface of the semi-conductor material is deprived of said transparent layer and is covered with a layer of a material having a low overvoltage for the reduction of a cation, of water or CO₂.

4. Product according to claim 3, wherein said layer of a material having a low overvoltage is selected from platinum and nickel.

5. Product according to any one of claims 1 and 2, in the form of a layer which comprises part of an electrode, characterized in that the semi-conductor material is deposited in a polycrystalline state on a conductive support in the form of a layer having a surface in contact with the conductive support and an opposite surface in contact with said transparent layer.

6. Product according to claim 5, characterized in that the surface of the conductive support which is not in contact with the semi-conductor material is coated with a layer of a material having a low overvoltage for the reduction of a cation, water or of CO₂.

7. Product according to claim 6, wherein said material having a low overvoltage is selected from platinum or nickel.

8. Method for the preparation of a product useful as a photocatalyst, characterized in that a transparent layer of ruthenium oxide (RuO₂), iridium oxide (IrO₂), or a mixture of ruthenium oxide (RuO₂) and iridium oxide (IrO₂) is formed on the surface intended to be illuminated of a semi-conductor material subject to photo-corrosion in order to protect the semi-conductor material against photo-corrosion.

9. The process of claim 8, wherein said transparent layer is formed by coating said semi-conductor material with at least one of ruthenium chloride (RuCl₃) and iridium chloride (IrCl₃) and heating the coated semi-conductor material in the presence of oxygen.

10. Method for producing at least one of electric power and a substance which is chemically transformable with release of energy, said method comprising exposure to electromagnetic radiation of a surface of a semi-conductor material positioned within an electrolyte, said semiconductor material being subject to photocorrosion, said surface being covered with a transparent layer of ruthenium oxide (RuO₂), iridium oxide (IrO₂), or a mixture thereof, which inhibits the photo-corrosion of said semi-conductor material.

11. Method according to claim 10, characterized in that a fuel is produced.

12. Method according to claim 10 or 9, characterized in that the semiconductor material is in the form of a layer which comprises part of an electrode and in that it is used as anode electrically connected to a separate cathode having a low overvoltage surface for the reduction of a cation, water or CO₂, both electrodes being immersed in an aqueous electrolyte.

13. Method according to claim 12, characterized in that the electrodes are arranged on each side of a wall so as to separate the reduced compound, from the oxidized compound.

14. Method according to claim 13, wherein said reduced compound is hydrogen and said oxidized compound is oxygen.

15. Method according to claim 11, characterized in that hydrogen is produced by oxidation-reduction of water or of a hydrohalic acid.

16. Method according to any one of the claims 10 to 15, characterized in that the semiconductor material is used in the form of particles, a mixture of the oxidized compound and of the reduced compound is collected, and in that subsequently both compounds are separated from each other.

17. Method according to claim 16, wherein said oxidized compound is oxygen and said reduced compound is hydrogen.

18. Method according to claim 15, wherein said hydrohalic acid is hydrobromic acid.

19. Method according to claim 11, characterized in that methanol is produced by oxidation-reduction of carbonic acid.

20. Method according to claim 10, characterized in that zinc or lead is produced by oxidation-reduction of a divalent zinc compound or a divalent lead compound, respectively.

21. Method for converting light energy into electric energy, comprising:

providing an anode in which a semi-conductor material is deposited in a polycrystalline state on a conductive support in the form of a layer having a surface in contact with the conductive support and an opposite surface in contact with a transparent layer of ruthenium oxide (RuO₂), iridium oxide (IrO₂), or a mixture thereof, said semi-conductor material being subject to photo-corrosion and said transparent layer inhibiting said photo-corrosion, and a cathode having a low overvoltage surface for the reduction of a cation, water or CO₂, both electrodes being electrically connected together through a useful load and both electrodes being immersed in an aqueous electrolyte comprising a bromine salt; and

illuminating the surface of said semi-conductor material in contact with said transparent layer to oxidize bromine anions to molecular bromine at said anode and reduce molecular bromine to bromine anions at said cathode.