Method for producing a catalyst support and compositions thereof

• US 7,390,767 B2
• Filed: 08/22/2006
• Issued: 06/24/2008
• Est. Priority Date: 03/07/1997
• Status: Expired due to Fees

• Current Assignee: Rice University
• Original Assignee: Rice University
• Inventors: Smalley, Richard E., Liu, Jie, Rinzler, Andrew G., Nikolaev, Pavel, Colbert, Daniel T., Thess, Andreas, Hafner, Jason H., Smith, Ken, Guo, Ting, Dai, Hongjie
• Primary Examiner(s): HENDRICKSON, STUART L
• Application Number:
  US11/507,973
• Publication Number:
  US 20080107586A1
• Time in Patent Office: 672 Days
• Field of Search: 977/848, 423/447.1, 502/185, 502/182
• US Class Current: 502/182
• CPC Class Codes: B01J 19/081 employing particle radiation or gamma-radiation
• CPC Class Codes: B01J 19/087 employing electric or magnetic energy
• CPC Class Codes: B01J 19/10 employing sonic or ultrasonic vibrations
• CPC Class Codes: B01J 19/121 Coherent waves, e.g. laser beams lasers per se H01S3/00
• CPC Class Codes: B01J 19/126 Microwaves
• CPC Class Codes: B01J 19/129 Radiofrequency
• CPC Class Codes: B01J 21/185 Carbon nanotubes carbon nanotubes per se C01B32/15
• CPC Class Codes: B01J 2219/00078 Fingers
• CPC Class Codes: B01J 2219/0892 involving catalytically active material
• CPC Class Codes: B01J 23/74 Iron group metals
• CPC Class Codes: B01J 23/755 Nickel
• CPC Class Codes: B01J 23/8913 Cobalt and noble metals
• CPC Class Codes: B01J 37/0238 via the gaseous phase-sublimation
• CPC Class Codes: B01J 37/349 making use of flames, plasmas or lasers
• CPC Class Codes: B82B 3/00 Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
• CPC Class Codes: C01B 2202/02 Single-walled nanotubes
• CPC Class Codes: C01B 32/156 After-treatment
• CPC Class Codes: C01B 32/162 characterised by catalysts
• CPC Class Codes: C01B 32/17 Purification
• CPC Class Codes: D01F 9/12 Carbon filaments; Apparatus specially adapted for the manufacture thereof
• CPC Class Codes: D01F 9/127 : by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
• CPC Class Codes: D21H 27/00 : Special paper not otherwise provided for, e.g. made by multi-step processes
• CPC Class Codes: G11B 9/1418 : Disposition or mounting of heads or record carriers G11B17/00 and G11B19/00 take precedence
• CPC Class Codes: G11B 9/1445 : switching at least one head in operating function; Controlling the relative spacing to keep the head operative, e.g. for allowing a tunnel current flow
• CPC Class Codes: G11B 9/1472 : characterised by the form
• CPC Class Codes: G11B 9/149 : characterised by the memorising material or structure
• CPC Class Codes: G11C 13/0014 : comprising cells based on organic memory material
• CPC Class Codes: G11C 13/0019 : comprising bio-molecules
• CPC Class Codes: G11C 13/025 : using fullerenes, e.g. C60, or nanotubes, e.g. carbon or silicon nanotubes
• CPC Class Codes: G11C 2213/16 : Memory cell being a nanotube, e.g. suspended nanotube
• CPC Class Codes: G11C 2213/71 : Three dimensional array
• CPC Class Codes: G11C 2213/81 : Array wherein the array conductors, e.g. word lines, bit lines, are made of nanowires
• CPC Class Codes: H01G 9/2059 : comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
• CPC Class Codes: H01L 31/0352 : characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
• CPC Class Codes: H01L 31/06 : characterised by potential barriers
• CPC Class Codes: H01L 31/18 : Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
• CPC Class Codes: H01M 10/0525 : Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 4/133 : Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: H01M 4/525 : of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• CPC Class Codes: H01M 4/583 : Carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: H01M 4/587 : for inserting or intercalating light metals
• CPC Class Codes: H01M 4/625 : Carbon or graphite
• CPC Class Codes: Y02E 10/542 : Dye sensitized solar cells
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries
• CPC Class Codes: Y02P 70/50 : Manufacturing or production processes characterised by the final manufactured product
• CPC Class Codes: Y10S 977/70 : Nanostructure
• CPC Class Codes: Y10S 977/742 : Carbon nanotubes, CNTs
• CPC Class Codes: Y10S 977/745 : having a modified surface
• CPC Class Codes: Y10S 977/748 : Modified with atoms or molecules bonded to the surface
• CPC Class Codes: Y10S 977/75 : Single-walled
• CPC Class Codes: Y10S 977/753 : with polymeric or organic binder
• CPC Class Codes: Y10S 977/789 : in array format
• CPC Class Codes: Y10S 977/842 : for carbon nanotubes or fullerenes
• CPC Class Codes: Y10S 977/843 : Gas phase catalytic growth, i.e. chemical vapor deposition
• CPC Class Codes: Y10S 977/845 : Purification or separation of fullerenes or nanotubes
• CPC Class Codes: Y10S 977/847 : Surface modifications, e.g. functionalization, coating
• CPC Class Codes: Y10S 977/848 : Tube end modifications, e.g. capping, joining, splicing
• CPC Class Codes: Y10S 977/849 : with scanning probe
• CPC Class Codes: Y10S 977/882 : Assembling of separate components, e.g. by attaching
• CPC Class Codes: Y10S 977/948 : Energy storage/generating using nanostructure, e.g. fuel cell, battery
• CPC Class Codes: Y10T 428/24058 : including grain, strips, or filamentary elements in respective layers or components in angular relation
• CPC Class Codes: Y10T 428/2918 : including free carbon or carbide or therewith [not as steel]
• CPC Class Codes: Y10T 428/292 : In coating or impregnation
• CPC Class Codes: Y10T 428/30 : Self-sustaining carbon mass or layer with impregnant or other layer

Abstract

This invention relates generally to a method for producing fullerene nanotube catalyst supports and compositions thereof. In one embodiment, fullerene nanotubes or fullerene nanotube structures can be employed as the support material. A transition metal catalyst is added to the fullerene nanotubes. In a preferred embodiment, the catalyst metal cluster is deposited on the open nanotube end by a docking process that insures optimum location for the subsequent growth reaction. The metal atoms may be subjected to reductive conditions.

Claims

1. A method for producing a catalyst support comprising:

(a) providing a plurality of fullerene nanotubes;

(b) contacting an end of at least some of the fullerene nanotubes of the plurality with at least one catalytic metal; and

(c) activating the catalytic metal.

2. The method of claim 1 wherein the catalyst metal is selected from the group consisting of transition metals, Group VIII metals, metals of the lanthanide series, metals of the actinide series, Iron (Fe), Nickel (Ni), Cobalt (Co), ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), platinum (Pt) and mixtures thereof.

3. The method of claim 1 further comprising removing an end cap from the end of at least some of the fullerene nanotubes.

4. The method of claim 3 wherein the end caps are removed by an oxidative treatment.

5. The method of claim 4 wherein the oxidative treatment comprises a technique selected from the group consisting of oxidative etching, electrochemical oxidative etching and combinations thereof.

6. The method of claim 4 wherein the oxidative treatment comprises the use of a chemical selected from the group consisting of nitric acid, oxygen, carbon dioxide and combinations thereof.

7. The method of claim 4 wherein the oxidative treatment is conducted at a temperature at most about 500°

C.

8. The method of claim 1 further comprising cutting the fullerene nanotubes.

9. The method of claim 1 wherein the catalytic metal is deposited on the fullerene nanotubes.

10. The method of claim 9 wherein the catalytic metal is deposited by a deposition method selected from the group consisting of deposition of a metal vapor in a vacuum, deposition of pre-formed catalyst particles, deposition of a catalyst precursor and combinations thereof.

11. The method of claim 10 wherein the deposition of the metal vapor is done by heating at least one wire comprising the catalytic metal.

12. The method of claim 10 wherein the catalyst precursor is a substance selected from the group consisting of an oxide, salt, metal complex and combinations thereof.

13. The method of claim 1 wherein the activating of the catalytic metal is by heating.

14. The method of claim 13 wherein the heating is localized at the ends of the fullerene nanotubes of the plurality.

15. The method of claim 13 wherein the heating is at a temperature in a range between about 500°

C. and about 1300°

C.

16. The method of claim 1 wherein the activating of the catalytic metal produces metal atom clusters comprising from about 10 to about 200 metal atoms.

17. The method of claim 16 wherein the metal atom clusters are located at the ends of the fullerene nanotubes.

18. The method of claim 1 wherein the plurality of fullerene nanotubes is a cross section of a previously-grown fiber.