Nanostructured titanium oxide material and its synthesis procedure

• US 7,645,439 B2
• Filed: 05/04/2005
• Issued: 01/12/2010
• Est. Priority Date: 10/10/2003
• Status: Active Grant

• Current Assignee: Instituto Mexicano Del Petrã³Leo (Gobierno Federal De Los Estados Unidos Mexicanos)
• Original Assignee: Instituto Mexicano Del Petrã³Leo (Gobierno Federal De Los Estados Unidos Mexicanos)
• Inventors: Lozada y Cassou, Marcelo, Angeles Chávez, Carlos, Cortés Jacome, María Antonia, López Salinas, Esteban, Toledo Antonio, José Antonio, Alvarez Ramírez, Fernando, Ferrat Torres, Gerardo, Flores Ortiz, Luis Francisco, Ruiz Morales, Yosadara
• Primary Examiner(s): Bos; Steven
• Assistant Examiner(s): Zimmer; Anthony J
• Application Number:
  US11/121,178
• Publication Number:
  US 20060078726A1
• Time in Patent Office: 1,714 Days
• Field of Search: 423/608, 423/609, 423/610, 423/611, 423/612, 423/613, 423/614, 977/734, 977/742, 977/811
• US Class Current: 423/609
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C01G 23/04 Oxides; Hydroxides
• CPC Class Codes: C01G 23/043 Titanium sub-oxides
• CPC Class Codes: C01G 23/047 Titanium dioxide
• CPC Class Codes: C01P 2002/76 by a space-group or by other symmetry indications
• CPC Class Codes: C01P 2002/77 by unit-cell parameters, atom positions or structure diagrams
• CPC Class Codes: C01P 2004/03 obtained by SEM
• CPC Class Codes: C01P 2004/04 obtained by TEM, STEM, STM or AFM
• CPC Class Codes: C01P 2004/13 Nanotubes
• CPC Class Codes: C01P 2004/16 Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
• CPC Class Codes: Y10S 977/811 Of specified metal oxide composition, e.g. conducting or semiconducting compositions such as ITO, ZnOx
• CPC Class Codes: Y10T 428/256 Heavy metal or aluminum or compound thereof
• CPC Class Codes: Y10T 428/2975 Tubular or cellular
• CPC Class Codes: Y10T 428/298 Physical dimension
• CPC Class Codes: Y10T 428/2982 Particulate matter [e.g., sphere, flake, etc.]

Abstract

Nanomaterials of the JT phase of the titanium oxide TiO_2-x, where 0≦x≦1 having as a building block a crystalline structure with an orthorhombic symmetry and described by at least one of the space groups 59 Pmmn, 63 Amma, 71 Immm or 63 Bmmb. These nanomaterials are in the form of nanofibers, nanowires, nanorods, nanoscrolls and/or nanotubes. The nanomaterials are obtained from a hydrogen titanate and/or a mixed sodium and hydrogen titanate precursor compound that is isostructural to the JT crystalline structure. The titanates are the hydrogenated, the protonated, the hydrated and/or the alkalinized phases of the JT crystalline phase that are obtained from titanium compounds such as titanium oxide with an anatase crystalline structure, amorphous titanium oxide, and titanium oxide with a rutile crystalline structure, and/or directly from the rutile mineral and/or from ilmenite. The titanates are submitted to dynamic thermal treatment in an inert, oxidizing or reducing atmosphere to produce the JT phase of the TiO_2-x, where 0≦x≦1 with an orthorhombic structure.

Claims

1. A thermally stable nanomaterial of titanium oxide of the formula TiO_2-x, where 0≦

x≦

1, having an orthorhombic crystalline lattice which is described by at least one of the space groups selected from the group consisting of 59 Pmmn, 63 Amma, 71 Immm and 63 Bmmb, and having a nanofibrilar and/or nanotubular morphology.

2. The titanium oxide nanomaterial of claim 1, wherein said orthorhombic crystalline lattice is described by the space group 59 Pmmn.

3. The titanium oxide nanomaterial of claim 1, wherein said orthorhombic crystalline lattice is described by the space group 63 Amma.

4. The titanium oxide nanomaterial of claim 1, wherein said orthorhombic crystalline lattice is described by the space group 71 Immm.

5. The titanium oxide nanomaterial of claim 1, wherein said orthorhombic crystalline lattice is described by the space group 63 Bmmb.

6. The titanium oxide nanomaterial of claim 1, wherein the cell parameters for said space groups of the orthorhombic crystalline lattice are , respectively:

a=from 0.283 to 0.324 nm, b=from 0.354 to 0.395 nm and c=from 0.695 to 0.735 nm for the space group 59 Pmmn, and a=from 0.283 to 0.324 nm, b=from 0.354 to 0.395 nm, c=from 1.453 to 1.408 nm, for the space groups 63 Amma, 71 Immm and 63 Bmmb;

with α

=β

=γ

=90°

.

7. The titanium oxide nanomaterial of claim 1, wherein x is between 0.1 and 0.95 with a high oxygen deficiency and an O/Ti ratio is between 1.0 and 2.

8. The titanium oxide nanomaterial of claim 1, wherein x is between 0.1 and 0.95.

9. The titanium oxide nanomaterial of claim 1, wherein said nanofibers and/or nanotubes have a diameter of between 3 and 50 nm and a length from 0.01 μ

m to 100 μ

m.

10. The titanium oxide nanomaterial of claim 1, wherein said nanofibers and mesoporous nanotubes have a homogeneous distribution of pores between 2 and 30 nm and a specific area between 5 and 500 m²/g.

11. The titanium oxide nanomaterial of claim 1, wherein said nanomaterial has a specific area between 100 and 400 m²/g and is thermally stable.

12. The titanium oxide nanomaterial of claim 1, wherein said nanotubular and/or nanofibrilar morphology is constituted of 1 to 50 structural layers with an inter-layer spacing between 0.695 and 0.735 nm, for the space group 59 Pmmn and from 0.704 to 0.727 nm, for the space groups 63 Amma, 71 Immm and 63 Bmmb.

13. The titanium oxide nanomaterial of claim 1, wherein said nanomaterial has a stable thermal nanotubular morphology at temperatures between 200°

C. and 500°

C.

14. A thermally stable nanomaterial of titanium oxide of the formula TiO_2-x, where 0≦

x≦

1, having an orthorhombic crystalline lattice which is described by at least one of the space groups selected from the group consisting of 59 Pmmn, 63 Amma, 71 Immm and 63 Bmmb, and having a nanofibrilar and/or nanotubular morphology constituted of piled structural layers, which are folded or rolled inwards into themselves, or formed from overlapped semitubes.

15. The titanium oxide nanomaterial of claim 14, wherein said orthorhombic crystalline lattice is described by the space group 59 Pmmn.

16. The titanium oxide nanomaterial of claim 14, wherein said orthorhombic crystalline lattice is described by the space group 63 Amma.

17. The titanium oxide nanomaterial of claim 14, wherein said orthorhombic crystalline lattice is described by the space group 71 Immm.

18. The titanium oxide nanomaterial of claim 14, wherein said orthorhombic crystalline lattice is described by the space group 63 Bmmb.

19. The titanium oxide nanomaterial of claim 14, wherein the cell parameters for said space groups of said orthorhombic crystalline lattice are, respectively:

a=from 0.283 to 0.324 nm, b=from 0.354 to 0.395 nm and c=from 0.695 to 0.735 nm for the space group 59 Pmmn, and a=from 0.283 to 0.324 nm, b=from 0.354 to 0.395 nm, c=from 1.453 to 1.408 nm, for the space groups 63 Amma, 71 Immm and 63 Bmmb;

with α

=β

=γ

=90°

.

20. The titanium oxide nanomaterial of claim 14, wherein x is between 0.1 and 0.95 with a high oxygen deficiency and an O/Ti ratio is between 1.0 and 2.

21. The titanium oxide nanomaterial of claim 14, wherein x is between 0.1 and 0.95.

22. The titanium oxide nanomaterial of claim 14, wherein said nanofibers and/or nanotubes have a diameter of between 3 and 50 nm and a length from 0.01 μ

m to 100 μ

m.

23. The titanium oxide nanomaterial of claim 14, wherein said nanofibers and mesoporous nanotubes have a homogeneous distribution of pores between 2 and 30 nm and a specific area between 5 and 500 m²/g.

24. The titanium oxide nanomaterial of claim 14, wherein said nanomaterial has a specific area between 100 and 400 m²/g and is thermally stable.

25. The titanium oxide nanomaterial of claim 14, wherein said nanotubular and/or nanofibrilar morphology is constituted of 1 to 50 structural layers with an inter-layer spacing between 0.695 and 0.735 nm, for the space group 59 Pmmn and from 0.704 to 0.727 nm, for the space groups 63 Amma, 71 Immm and 63 Bmmb.

26. The titanium oxide nanomaterial of claim 14, wherein said nanomaterial has a stable thermal nanotubular morphology at temperatures between 200°

C. and 500°

C.