Monolithic catalyst system for the photolysis of water

• US 8,883,671 B2
• Filed: 10/31/2008
• Issued: 11/11/2014
• Est. Priority Date: 10/31/2007
• Status: Active Grant

• Current Assignee: CFSO GmbH
• Original Assignee: CFSO GmbH
• Inventors: Obenland, Sigrid, Fischer, Christian
• Primary Examiner(s): Zimmer, Anthony J
• Application Number:
  US12/734,330
• Publication Number:
  US 20110220484A1
• Time in Patent Office: 2,202 Days
• Field of Search: 502150-173, 204/157.5, 204/157.52, 423/579, 423/647.7, 423/648.1, 423/657
• US Class Current: 502/150
• CPC Class Codes: B01J 21/063 Titanium; Oxides or hydroxides thereof
• CPC Class Codes: B01J 2231/62 Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
• CPC Class Codes: B01J 2231/70 Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
• CPC Class Codes: B01J 23/26 Chromium
• CPC Class Codes: B01J 23/42 Platinum
• CPC Class Codes: B01J 23/52 Gold
• CPC Class Codes: B01J 23/6527 Tungsten
• CPC Class Codes: B01J 2531/0216 Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
• CPC Class Codes: B01J 2531/72 Manganese
• CPC Class Codes: B01J 2531/821 Ruthenium
• CPC Class Codes: B01J 2531/824 Palladium
• CPC Class Codes: B01J 27/045 Platinum group metals
• CPC Class Codes: B01J 31/1815 with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
• CPC Class Codes: B01J 31/1865 Phosphonites (RP(OR)2) , their isomeric phosphinates (R2(RO)P=O) and RO-substitution derivatives thereof
• CPC Class Codes: B01J 31/2226 Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
• CPC Class Codes: B01J 35/19 Catalysts containing parts with different compositions
• CPC Class Codes: B01J 35/23 in a colloidal state
• CPC Class Codes: B01J 35/33 Electric or magnetic properties
• CPC Class Codes: B01J 35/39 Photocatalytic properties
• CPC Class Codes: C01B 3/042 Decomposition of water
• CPC Class Codes: C25B 1/55 : Photoelectrolysis
• CPC Class Codes: Y02E 60/36 : Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

A monolithic catalyst system for the cleavage of water into hydrogen and oxygen comprises a first photoactive material capable by itself or together with an auxiliary material and/or an auxiliary catalyst when irradiated with light having a wavelength≧420 nm of generating oxygen and protons from water, and a second photoactive material capable by itself or together with an auxiliary material and/or an auxiliary catalyst when irradiated with light having a wavelength≧420 nm of reducing protons in water to hydrogen. The first and second photoactive materials are in electrical contact via an electron-conducting material.

Claims

1. A monolithic catalyst system for the cleavage of water into hydrogen and oxygen with the aid of light, wherein the catalyst system comprises (a) a first photoactive material which, when irradiated with light having a wavelength≧

420 nm, is capable of generating oxygen and protons from water either by itself or together with at least one of an auxiliary material and an auxiliary catalyst, and (b) a second photoactive material which, when irradiated with light having a wavelength≧

420 nm, is capable of reducing protons in water to hydrogen either by itself or together with at least one of an auxiliary material and an auxiliary catalyst, (a) and (b) being in electrical contact via (c) one or more electron-conducting materials.

2. The catalyst system of claim 1, wherein the wavelength is ≧

450 nm.

3. The catalyst system of claim 1, wherein the system comprises one or more auxiliary materials and/or catalysts which are in association with at least one of (a) and (b).

4. The catalyst system of claim 1, wherein (c) comprises at least one of a metal, a metal alloy, and an oxidic electron-conducting material.

5. The catalyst system of claim 1, wherein the system comprises a substrate.

6. The monolithic catalyst system of claim 1, wherein (a) comprises one or more materials selected from optionally doped oxide- and/or sulphide-containing materials, complexes and clusters comprising at least one of a noble metal and a transition metal, and photoactive polymeric materials.

7. The catalyst system of claim 1, wherein (b) comprises one or more materials selected from metal-containing complexes, organic compounds having an extended π

system, oxide and/or oxynitride containing materials, phosphide, arsenide, antimonide, sulphide and/or selenide containing materials, and photosemiconducting polymers.

8. The catalyst system of claim 1, wherein at least one of (a) and (b) is bound to (c) by a functional group.

9. The catalyst system of claim 1, wherein the system comprises a plane multilayer structure, one side of the structure comprising (a) and the other side of the structure comprising (b), or one side of the structure comprising both (a) and (b).

10. A method of generating oxygen and hydrogen from water with the aid of light and a catalyst system, wherein the method comprises contacting a monolithic catalyst system comprising (a) a first photoactive material which, when irradiated with light having a wavelength≧

420 nm, is capable of generating oxygen and protons from water either by itself or together with at least one of an auxiliary material and an auxiliary catalyst, and (b) a second photoactive material which, when irradiated with light having a wavelength≧

420 nm, is capable of reducing protons in water to hydrogen either by itself or together with at least one of an auxiliary material and an auxiliary catalyst, (a) and (b) being in electrical contact via (c) one or more electron-conducting materials, with water or an aqueous fluid or solution at a first location comprising the first photoactive material or at least one of an auxiliary material and an auxiliary catalyst associated therewith, and at a second location comprising the second photoactive material or at least one of an auxiliary material and an auxiliary catalyst associated therewith, and thereafter irradiating with light the water or aqueous fluid or solution in contact with the first location and the water or aqueous fluid or solution in contact with the second location, the first and second locations being in contact with each other such that protons can migrate from the first location to the second location.

11. The method of claim 10, wherein the light comprises sunlight.

12. The method of claim 10, wherein the first location and the second location are separated from each other by a membrane that is permeable only for protons and water.

13. The method of claim 10, wherein the first location is directly irradiated with light.

14. The method of claim 10, wherein the second location is directly irradiated with light.

15. The method of claim 10, wherein the first location and the second location location are directly irradiated with light.

16. The method of claim 10, wherein at least one of oxygen and hydrogen are collected intermittently or continuously.