Photoelectrolysis of water by solar radiation

• US 4,011,149 A
• Filed: 11/17/1975
• Issued: 03/08/1977
• Est. Priority Date: 11/17/1975
• Status: Expired due to Term

• Current Assignee: Allied Chemical Corporation (Honeywell International Inc.)
• Original Assignee: Allied Chemical Corporation (Honeywell International Inc.)
• Inventors: Nozik, Arthur Jack
• Primary Examiner(s): Mack, John H.
• Assistant Examiner(s): Weisstuch, Aaron
• Application Number:
  US05/632,557
• Time in Patent Office: 477 Days
• Field of Search: 204/129, 204/278, 250/527, 136/89
• US Class Current: 205/340
• CPC Class Codes: C25B 1/55 Photoelectrolysis
• CPC Class Codes: H01G 9/20 Light-sensitive devices
• CPC Class Codes: Y02E 60/36 Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
• CPC Class Codes: Y02P 20/129 Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
• CPC Class Codes: Y02P 20/133 Renewable energy sources, e.g. sunlight
• CPC Class Codes: Y10S 204/03 Auxiliary internally generated electrical energy

Abstract

Photoelectrolysis of water by solar radiation to produce hydrogen is achieved using semiconducting thin film electrodes. The cell comprises (a) an electrode comprising at least one thin film semiconducting layer disposed on a substrate, each layer having a bandgap which ranges from about 1.3 to 4.0 eV; (b) a counter-electrode; (c) an electrolyte disposed between the thin film semiconducting electrode and the counter-electrode; (d) external bias means between the electrode for biasing the electrode with from 0 to about 1 V; and (e) means for collecting hydrogen produced.

Claims

1. A photoelectrolysis cell for producing hydrogen from solar radiation comprising

a. an electrode comprising an outer, chemically inert thin film semiconducting layer supported on at least one inner thin film semiconducting layer of some conductivity type as said outer layer, which is disposed on a supporting conductive substrate, each layer having a bandgap which ranges from about 1.3 to 4.0 eV;

b. a counter-electrode;

c. means for retaining an electrolyte disposed between the electrode and the counter-electrode;

d. external bias means between the electrode and the counter-electrode for biasing the electrode with from 0 to about -1 V; and

e. means for collecting hydrogen produced.

2. The cell of claim 1 in which the electrode comprises at least one suitably doped n-type composition selected from the group consisting of TiO₂, In₂ O₃, SnO₂, GaAs, GaP, CdS, Si and MTiO₃, where M is at least one element selected from the group consisting of La, Ba, Sr, the rare earth elements and the transition metal elements.

3. The cell of claim 2 in which the electrode comprises an outer layer of n-type TiO₂ and an inner layer of at least one n-type composition selected from the group consisting of CdS, GaP, GaAs, CdTe and Si, with the bandgap of each layer ranging from about 1. 3 to 4.0 eV.

4. The cell of claim 1 in which the counter-electrode comprises at least one thin film semiconducting layer having a conductivity type opposite so that of the thin film semiconducting electrode and in which the sum of the bandgaps for all photoactive layers of both electrodes ranges from 1.3 to 5.0 eV.

5. The cell of claim 4 in which the counter-electrode comrises a suitably doped p-type composition selected from the group consisting of GaAs, GaP, CdTe, CuInS₂, InP, ZnSe, Cu₂ S and Si.

6. The cell of claim 1 in which the counter-electrode is metallic.

7. The cell of claim 6 in which the electrode comprises at least one n-type semiconducting composition and the bias applied ranges from 0 to about +1 V.

8. The cell of claim 6 in which the electrode comprises at least one p-type semiconducting composition and the bias applied ranges from 0 to about -1 V.

9. The cell of claim 8 in which the electrode comprises at least one suitably doped p-type composition selected from the group consisting of GaAs, GaP, CdTe, CuInS₂, InP, ZnSe, Cu₂ S and Si.

10. The cell of claim 1 in which the substrate comprises a transparent electrically conducting material selected from the group consisting of Cd₂ SnO₄ and suitably doped In₂ O₃ and SnO₂.

11. A process for producing hydrogen from solar radiation comprising

a. exposing to solar radiation an electrode in contact with an electrolyte in turn having a counter-electrode in contact therewith, said electrode comprising an outer, chemically inert thin film semiconducting layer supported on at least one inner thin film semiconducting layer of some conductivity type as said outer layer, said layers being disposed on a supporting conducting substrate, each layer having a bandgap which ranges from about 1.3 to 4.0 eV;

b. applying a bias between the electrode and the counterelectrode of from 0 to about - 1 V; and

c. collecting hydrogen produced.

12. The process of claim 11 in which the electrode comprises at least one suitably doped n-type composition selected from the group consisting of TiO₂, In₂ O₃, SnO₂, GaAs, GaP, CdS, Si and MTiO₃, where M is at least one element selected from the group consisting of La, Ba, Sr, the rare earth elements and the transition metal elements.

13. The process of claim 12 in which the electrode comprises an outer layer of n-type TiO₂ and an inner layer of at least one n-type composition selected from the group consisting of CdS, GaP, GaAs, CdTe and Si, with the bandgap of each layer ranging from about 1.3 to 4.0 eV.

14. The process of claim 12 in which the counterelectrode comprises at least one thin film semiconducting layer having a conductivity type opposite to that of the thin film semiconducting electrode and in which the sum of the bandgaps for all photoactive layers of both electrodes ranges from about 1.3 to 5.0 eV.

15. The process of claim 14 in which the counter-electrode comprises at least one suitably doped p-type composition selected from the group consisting of GaAs, GaP, CdTe, CuInS₂, InP, ZnSe, Cu₂ S and Si.

16. The process of claim 11 in which the counter-electrode is metallic.

17. The process of claim 16 in which the electrode comprises at least one n-type semiconducting composition and the bias applied ranges from 0 to about +1 V.

18. The process of claim 16 in which the electrode comprises at least one p-type semiconducting composition and the bias applied ranges from 0 to about -1 V.

19. The process of claim 18 in which the electrode comprises at least one suitably doped p-type composition selected from the group consisting of GaAs, GaP, CdTe, CuInS₂, InP, ZnSe, Cu₂ S and Si.

20. The process of claim 11 in which the substrate comprises a transparent electrically conducting material selected from the group consisting of Cd₂ SnO₄ and suitably doped In₂ O₃ and SnO₂.

21. The process of claim 11 in which the electrolyte comprises an aqueous solution having a specific conductivity of at least about 10^-3 ohm^-1cm-1.

22. The process of claim 11 in which the electrolyte comprises a solid polymer electrolyte having a specific conductivity of at least about 10^-3 ohm^-1cm-1.

23. The process of claim 11 in which the electrolyte includes a photosensitive dye.