Organic conductive films for semiconductor electrodes

• US 4,461,691 A
• Filed: 02/10/1983
• Issued: 07/24/1984
• Est. Priority Date: 02/10/1983
• Status: Expired due to Fees

• Current Assignee: United States Of America As Represented By The Department Of Energy
• Original Assignee: United States Department of Energy
• Inventors: Frank, Arthur J.
• Primary Examiner(s): Weisstuch, Aaron
• Application Number:
  US06/465,418
• Time in Patent Office: 530 Days
• Field of Search: 204/290 R, 204/242, 204/DIG. 3, 204/129, 204/78, 204/79, 429/111
• US Class Current: 204/242
• 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: Y10S 204/03 Auxiliary internally generated electrical energy

Abstract

According to the present invention, improved electrodes overcoated with conductive polymer films and preselected catalysts are provided. The electrodes typically comprise an inorganic semiconductor overcoated with a charge conductive polymer film comprising a charge conductive polymer in or on which is a catalyst or charge-relaying agent.

Claims

1. An electrode for use in photoelectrochemical cells to effect generating fuels and useful chemicals, said electrode comprising:

(a) a semiconductor overcoated with a conductive film capable of transporting electrons and holes and comprising a charge conductive polymer for preventing photogenerated holes and electrons from substantially reacting with said electrode; and

(b) at least one redox enhancer for catalyzing certain chemical reactions required to generate said fuels and useful chemicals and for substantially preventing said photogenerated holes and electrons from reacting with said conductive polymer, said redox enhancer being incorporated within or attached to the surface of said conductive polymer, said redox enhancer being selected from a group consisting of charge-relaying agents.

2. An electrode according to claim 1 wherein said redox enhancer is a catalyst.

3. An electrode according to claim 1 wherein said film further comprises at least one catalyst and at least one charge relaying agent.

4. An electrode according to claim 1 wherein said semiconductor is n-type.

5. An electrode according to claim 1 wherein said semiconductor is p-type.

6. An electrode according to claim 1 wherein said conductive polymer is selected from the group consisting of heterocyclic aromatic polymers with extended pi-bonding, phthalocyaninatometal polymers with organic bridging ligands containing delocalized pi-electrons, bridged stacked metallophthalocyanines where pi-orbital overlap occurs at the phthalocyanine rings, and conductive polymers derived from the addition of metals or graphite particles to organic polymers.

7. An electrode according to claim 1 wherein said redox enhancer is on the surface of said film.

8. An electrode according to claim 1 wherein said redox enhancer is intermixed with said polymer.

9. A photoelectrochemical cell for generating fuels and useful chemicals, said photoelectrochemical cell comprising:

(a) at least one photoelectrode and an electrolyte containing at least two redox couples wherein said photoelectrode comprises a semiconductor overcoated with a conductive film capable of transporting electrons and holes and comprising a charge conductive polymer for substantially preventing photogenerated holes and electrons from reacting with said photoelectrode; and

(b) a redox enhancer for catalyzing certain chemical reactions required to generate said fuels and useful chemicals and for substantially preventing said photogenerated holes and electrodes from reacting with said conductive polymer, said redox enhancer being incorporated within or attached to the surface of said conductive polymer, said redox enhancer being selected from a group consisting of catalysts for said redox couples and charge-relaying agents.

10. A cell according to claim 9 wherein said redox enhancer is intermixed with said polymer.

11. A cell according to claim 9 wherein said redox enhancer is on the surface of said film.

12. A cell according to claim 9 wherein said redox couples are selected from the group consisting of (a) H⁺ /H₂ and O₂ /H₂ O, (b) CO₂ /HCOOH and O₂ /H₂ O, (c) CO₂ /HCHO and O₂ /H₂ O, (d) CO₂ /CH₃ OH and O₂ /H₂ O, (e) CO₂ /CH₄ and O₂ /H₂ O, (f) N₂ /NH₃ and O₂ /H₂ O, and (g) CO₂ /C₆ H₁₂ O₆ and O₂ /H₂ O.

13. A cell according to claim 9 wherein said semiconductor has a bandgap between 0.5 and 3.0 eV.

14. A cell according to claim 9 wherein said one photoelectrode is n-type.

15. A cell according to claim 9 wherein said photoelectrode material is selected from the group consisting of amorphous material, thin film material, single crystal material, and multiple layered material.

16. A cell according to claim 14 further comprising a second electrode which is metal.

17. A cell according to claim 14 further comprising a second electrode which is a p-type photoelectrode.

18. A cell according to claim 9 wherein said one photoelectrode is p-type.

19. A cell according to claim 18 further comprising a second electrode which is metal.

20. A cell according to claim 9 wherein said one photoelectrode comprises a particulate semiconductor.