Photocatalytic film for the cleavage of water into hydrogen and oxygen

• US 7,271,334 B2
• Filed: 07/29/2001
• Issued: 09/18/2007
• Est. Priority Date: 07/29/2000
• Status: Expired due to Fees

• Current Assignee: Hydrogen Solar Ltd.
• Original Assignee: The Hydrogen Solar Production Company Limited
• Inventors: Gratzel, Michael, Thampi, Ravindranathan
• Primary Examiner(s): Nguyen; Nam
• Assistant Examiner(s): Barton; Jeffrey
• Application Number:
  US10/343,272
• Publication Number:
  US 20030121543A1
• Time in Patent Office: 2,242 Days
• Field of Search: 136243-265, 204155-15821, 204/242, 204/258
• US Class Current: 136/263
• CPC Class Codes: B01J 35/30 characterised by their physical properties
• CPC Class Codes: B01J 35/39 Photocatalytic properties
• CPC Class Codes: C25B 1/55 Photoelectrolysis
• CPC Class Codes: H01G 9/2027 comprising an oxide semiconductor electrode
• CPC Class Codes: H01M 14/005 Photoelectrochemical storage cells light sensitive devices H01G9/20, semiconductors sensitive to light H01L31/00
• CPC Class Codes: H01M 4/52 of nickel, cobalt or iron
• CPC Class Codes: H01M 4/64 Carriers or collectors
• CPC Class Codes: Y02E 10/542 Dye sensitized solar cells
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• 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

Abstract

The Photocatalytic film of semiconducting iron oxide (Fe₂O₃), contains an n-dopant, or a mixture of n-dopants, or a p-dopant or a mixture of p-dopants. Electrode consists of a substrate, with one or more films or photocatalytic arrangements of film of semiconducting n-doped or p-doped iron oxide (Fe₂O₃) e.g. on the surface of one side of the substrate or on the surface of different sides. The photoelectrochemical cell comprises electrodes with a film or with films of the n-doped or p-doped semiconducting iron oxide (Fe₂O₃). The semiconducting iron oxide (Fe₂O₃) film can be manufactured with a spray pyrolysis process or a sol gel process. The system for the direct cleavage of water with visible light, into hydrogen and oxygen the system comprises one or more of the photoelectrochemical cells with photocatalytic films. The system can be a tandem cell system, comprising the photoelectrochemical cell with the doped iron oxide (Fe₂O₃) film.

Claims

1. A system for the direct cleavage of water into hydrogen and oxygen using visible light, the system comprising a tandem cell consisting of two superimposed and electrically connected photoelectrochemical cells;

a photoactive material present in a top compartment of the top cell being a film or an arrangement of layers of films of iron oxide deposited on a conducting glass and placed in contact with an aqueous electrolyte solution;

said oxide comprising an n-dopant, a p-dopant, a mix of n-dopants or a mix of p-dopants and absorbing a blue and a green part of the solar emission spectrum to generate oxygen and protons from water and transmitting a yellow and a red part of the solar emission spectrum to a bottom photoelectrochemical cell, mounted, in the direction of the light, behind the top cell and comprising a dye sensitized photovoltaic film;

said bottom cell converting the yellow, red and near infrared portion of the light in particular sunlight, to drive the reduction of the protons, produced in the top cell during the water oxidation process, said reduction of protons to hydrogen gas taking place in an electrolyte compartment mounted behind the bottom cell and being separated from the top cell compartment where oxygen is evolved by a glass frit or an ion conducting membrane.

2. A system for the cleavage of water by light, the system comprising:

a first photocell comprising photoactive semiconducting iron oxide which generates oxygen and protons when immersed in an aqueous electrolyte and illuminated by light of a first range of wavelengths; and

a second photocell connected electrically to said first photocell and to an electrode, the second photocell comprising a dye sensitized mesoporous photovoltaic film which generates a voltage at said electrode when said dye sensitized mesoporous photovoltaic film is illuminated by light of a second different range of wavelengths and the electrode is immersed in the aqueous electrolyte;

wherein said voltage reduces said protons to hydrogen; and

said semiconducting iron oxide comprises an n-dopant, a p-dopant, a mix of n-dopants or a mix of p-dopants.

3. A system according to claim 2, wherein said first range of wavelengths is generally that of blue and/or green light.

4. A system according to claim 2, wherein said dye sensitized mesoporous photovoltaic film is titanium dioxide, and said second range of wavelengths is generally that of yellow and/or red and/or near infra-red light.

5. A system according to claim 2, wherein said semiconducting oxide is deposited on a conducting substrate or conducting glass.

6. A system according to claim 2, wherein said aqueous electrolyte comprises seawater.

7. A system according to claim 2, wherein said first and second photocells are arranged one behind the other, so that said first photocell is superimposed on said second photocell.

8. A system according to claim 2, further comprising a chamber for holding the aqueous electrolyte, the chamber comprising first and second compartments in fluid communication with one another, said first photocell being immersed in electrolyte in said first compartment, and said electrode being immersed in electrolyte in said second compartment, the arrangement being such that oxygen is evolved for collection in said first compartment and hydrogen is evolved for collection in said second compartment.

9. A system according to claim 8, wherein the first and second compartments are separated from one another by means of a glass frit or an ion conducting membrane.

10. A system according to claim 2, further comprising a chamber for holding the aqueous electrolyte, said first photocell and said electrode being immersed in said electrolyte in said chamber, the arrangement being such that hydrogen and oxygen are evolved in said chamber.