Catalysts and processes for their preparation

• US 7,572,750 B2
• Filed: 02/11/2003
• Issued: 08/11/2009
• Est. Priority Date: 02/11/2002
• Status: Expired due to Fees

• Current Assignee: Aquahydrex, Inc.
• Original Assignee: University Of Wollongong
• Inventors: Chen, Jun, Wallace, Gordon G., Swiegers, Gerhard F., Too, Chee O.
• Primary Examiner(s): Lorengo; Jerry
• Assistant Examiner(s): McDonough; James E
• Application Number:
  US10/504,167
• Publication Number:
  US 20050164297A1
• Time in Patent Office: 2,373 Days
• Field of Search: 204/290.11, 204/290.14, 20440301-40315, 204636-638, 502/159, 502/164, 502/167, 502/102, 502/150, 502/523, 548/402, 429 40- 46, 436/19, 205/775
• US Class Current: 502/102
• CPC Class Codes: B01J 2531/842 Iron
• CPC Class Codes: B01J 31/069 Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups nitrogen containing groups on mineral substrates B01J31/0254; organometallic polymers B01J31/123; coordination complexes immobilised on an inorganic support B01J31/1616; coordination polymers, e.g. metal-organic frameworks B01J31/1691
• CPC Class Codes: B01J 31/2295 Cyclic compounds, e.g. cyclopentadienyls
• CPC Class Codes: C08G 61/124 with a five-membered ring containing one nitrogen atom in the ring
• CPC Class Codes: C25B 11/04 characterised by the material
• CPC Class Codes: H01M 8/16 Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
• CPC Class Codes: Y02E 60/50 Fuel cells

Abstract

A hybrid homogeneous-heterogeneous catalyst containing catalytic groups, wherein the catalytic activity of the catalyst is largely provided as a result of the interaction of catalytic groups in a suitable proximity and disposition to other catalytic groups, the proximity and disposition resulting from statistical considerations, wherein an example of such catalyst is a polypyrrole-ferrocene monosulfate represented by Formula IV.

Claims

1. An artificial hybrid homogeneous-heterogeneous catalyst for the reaction and/or production of small gaseous molecules, comprising:

a support substrate;

first catalytic groups; and

second catalytic groups,

wherein said first catalytic groups and said second catalytic groups may be the same or different, wherein at least some of either of said first catalytic groups and second catalytic groups is supported by the support substrate;

wherein said first catalytic groups and said second catalytic groups are present in a catalytically effective amount when arranged so that at least some of the first catalytic groups are located proximate and oriented relative to the second catalytic groups so that said first and second catalytic groups together provide a catalytic effect for the reaction and/or production of small gaseous molecules,

wherein the first catalytic groups are not covalently bound to the second catalytic groups within the same molecule;

wherein the first catalytic groups and the second catalytic groups do not together provide any catalytic effect for the reaction and/or production of small gaseous molecules when dispersed in a homogenous solution; and

wherein either the product and/or the reactant are a small gaseous molecule.

2. The artificial hybrid homogeneous-heterogeneous catalyst of claim 1, wherein an increase only of X in the number of catalytic groups provided to the support substrate during formation of the catalyst causes an increase of Y in the catalytic effect, where Y is greater than X due to an increase in the likelihood that the catalytic groups are located proximate and oriented relative to one another so as to be catalytically effective.

3. The artificial hybrid homogeneous-heterogeneous catalyst of claim 1, wherein the first catalytic groups and the second catalytic groups facilitate the reaction of one or more reagents thereby providing a catalytic effect and the catalytic effect at a constant concentration M of the one or more reagents is increased by a factor X, wherein X is greater than 1, upon application of conditions, during the formation of the catalyst, which cause a change in the likelihood that catalytic groups will be located proximate and oriented relative to one another so as to be catalytically effective.

4. The artificial hybrid homogeneous-heterogeneous catalyst of claim 3, wherein the conditions are selected from at least one member of the group consisting of:

the concentration of first and second catalytic groups provided to the support substrate;

the polarity of a solute which contacts the support substrate;

the acidity of the solute which contacts the support substrate;

supramolecular interactions between the catalytic groups; and

the temperature of the solute in which the support substrate.

5. The artificial hybrid homogeneous-heterogeneous catalyst of claim 1, wherein the support substrate is a porous framework.

6. The artificial hybrid homogeneous-heterogeneous catalyst of claim 5, wherein the porous framework is a conducting polymer.

7. The artificial hybrid homogeneous-heterogeneous catalyst of claim 6, wherein the conducting polymer is selected from the group consisting of polypyrrole, polyaniline and polythiophene.

8. The artificial hybrid homogeneous-heterogeneous catalyst of claim 1, wherein the first catalytic groups are a ferrocene and the second catalytic groups are a ferrocene.

9. The artificial hybrid homogeneous-heterogeneous catalyst of claim 8, wherein at least one of the ferrocene is substituted with a substituent selected from the group including C_3-20 alkyl, C_3-20 acyl, —

SO₃⁻

, —

SO₃²⁻

, —

SO₄²⁻

and —

PO₄³⁻

.

10. The artificial hybrid catalyst of claim 8, wherein the ferrocenes are coated onto the surface of an electrode substrate as part of a polymeric coating.

11. The artificial hybrid catalyst of claim 10, wherein the polymeric coating is a conducting electroactive polymer containing anionic ferrocenes as counter ions.

12. The artificial hybrid homogeneous-heterogeneous catalyst of claim 1, wherein said catalyst comprises a polypyrrole-ferrocene monosulfonate represented by formula (IV)

13. The artificial hybrid homogeneous-heterogeneous catalyst of claim 12, wherein said catalyst comprises a polypyrrole-ferrocene represented by formula (IV):