Mesoporous materials and processes for preparation thereof

Patent metadata

Field	Value
Publication number	US-10046313-B2
Application number	US-201414891228-A
Country	US
Kind code	B2
Filing date	May 8, 2014
Priority date	May 13, 2013
Publication date	Aug 14, 2018
Grant date	Aug 14, 2018

Abstract

A process for preparing a mesoporous material, e.g., transition metal oxide, sulfide, selenide or telluride, Lanthanide metal oxide, sulfide, selenide or telluride, a post-transition metal oxide, sulfide, selenide or telluride, and metalloid oxide, sulfide, selenide or telluride. The process comprises providing a micellar solution comprising a metal precursor, an interface modifier, a hydrotropic or lyotropic ion precursor, and a surfactant; and heating the micellar solution at a temperature and for a period of time sufficient to form the mesoporous material. A mesoporous material prepared by the above process. A method of controlling nano-sized wall crystallinity and mesoporosity in mesoporous materials. The method comprises providing a micellar solution comprising a metal precursor, an interface modifier, a hydrotropic or lyotropic ion precursor, and a surfactant; and heating the micellar solution at a temperature and for a period of time sufficient to control nano-sized wall crystallinity and mesoporosity in the mesoporous materials. Mesoporous materials and a method of tuning structural properties of mesoporous materials.

First claim

What is claimed is:

1. A process for preparing a mesoporous material, said process comprising:
preparing an acidic solution comprising nitric acid, one or more metal precursors, one or more surfactants, one or more interface modifiers, and optionally one or more lyotropic ion precursors or one or more organic and/or inorganic additives, wherein water is eliminated or minimized to prevent aggregation of metal oxide clusters;
forming inverse micelles, said micellar solution including a dispersion of micelles in which at least a portion of said one or more metal precursors are solubilized in the micelles; and
heating the micellar solution at a temperature and for a period of time sufficient to form the mesoporous material.

2. The process of claim 1 , wherein the process is a sol-gel micelle based process.

3. The process of claim 1 , wherein micellization and inter-micellar interaction are controlled by said one or more metal precursors, one or more surfactants, one or more interface modifiers, one or more lyotropic ion precursors, and optionally one or more organic and/or inorganic additives.

4. The process of claim 1 , wherein the heating step comprises:
heating the micellar solution at a temperature and for a period of time sufficient to form a dried powder; and
heating the dried powder at a temperature and for a period of time sufficient to form the mesoporous material.

5. The process of claim 4 , wherein the micellar solution is heated sequentially as follows:
at a temperature from about 75° C. to about 150° C. for a period from about 1 to about 12 hours; and
at a temperature from about 40° C. to about 80° C. for a period from about 1 to about 12 hours.

6. The process of claim 4 , wherein the dried powder is heated sequentially as follows:
at a temperature from about 100° C. to about 200° C. for a period from about 2 to about 20 hours;
at a temperature from about 200° C. to about 300° C. for a period from about 1 to about 10 hours;
at a temperature from about 300° C. to about 400° C. for a period from about 1 to about 8 hours;
at a temperature from about 400° C. to about 500° C. for a period from about 0.5 to about 4 hours; and
at a temperature from about 500° C. to about 600° C. for a period from about 0.1 to about 2 hours.

7. The process of claim 4 , wherein the dried powder is heated sequentially as follows:
at a temperature of about 150° C. for a period of about 12 hours;
at a temperature of about 250° C. for a period of about 4 hours;
at a temperature of about 350° C. for a period of about 3 hours;
at a temperature of about 450° C. for a period of about 2 hours; and
at a temperature of about 550° C. for a period of about 1 hour.

8. The process of claim 1 , wherein the mesoporous material comprises an oxide, a sulfide, a selenide or a telluride of the following:
a transition metal selected from the group consisting of Cr, Zr, Nb, Hf and Ta;
a Lanthanide selected from the group consisting of Nd, Sm, Ce and Gd;
a post-transition metal comprising Sn; or
a mixed metal or a solid acid selected from the group consisting of P Zr, W Zr, S Ti, Sn Zr and S Zr.

9. The process of claim 1 , wherein the mesoporous material comprises at least one of:
a transition metal oxide selected from the group consisting of Cr 2 O 3 , ZrO 2 , Nb 2 O 5 , HfO 2 and Ta 2 O 5 ;
a post-transition metal oxide comprising SnO 2 ; or
a Lanthanide oxide selected from the group consisting of CeO 2 , Nd 2 O 3 , Sm 2 O 3 and Gd 2 O 3 .

10. The process of claim 1 , wherein the mesoporous material is selected from the group consisting of:
a transition metal oxide, sulfide, selenide or telluride;
a Lanthanide metal oxide, sulfide, selenide or telluride;
a post-transition metal oxide, sulfide, selenide or telluride;
a metalloid oxide, sulfide, selenide or telluride; and mixtures thereof.

11. The process of claim 10 , wherein the transition metal oxide, sulfide, selenide or telluride comprises a Group 3-12 transition metal oxide, sulfide, selenide or telluride.

12. The process of claim 11 , wherein the Group 3-12 transition metal oxide, sulfide, selenide or telluride is selected from the group consisting of a Sc, Y, La, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd and Hg oxide, sulfide, selenide or telluride.

13. The process of claim 10 , wherein the transition metal oxide is selected from a Group 6-12 transition metal oxide, sulfide, selenide or telluride.

14. The process of claim 13 , wherein the Group 6-12 transition metal oxide, sulfide, selenide or telluride is selected from the group consisting of a Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd and Hg oxide, sulfide, selenide or telluride.

15. The process of claim 10 , wherein
the Lanthanide metal oxide, sulfide, selenide or telluride is selected from the group consisting of a La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu oxide, sulfide, selenide or telluride;
the post-transition metal oxide, sulfide, selenide or telluride is selected from the group consisting of an Al, Ga, In, TI, Sn, Pb and Bi oxide, sulfide, selenide or telluride; and
the metalloid oxide, sulfide, selenide or telluride is selected from the group consisting of a B, Si, Ge, As, Sb, Te, Po and At oxide, sulfide, selenide or telluride.

16. The process of claim 1 , wherein
the one or more metal precursors are selected from the group consisting of a metal halide, a metal phosphate, a metal acetate, a metal nitrate, a metal alkoxide, and a M x O y oxide that is capable of dissolving in HNO 3 ;
the one or more interface modifiers comprise an aliphatic, alicyclic or aromatic hydrocarbon of between about 1 and about 20 carbon atoms, or mixtures thereof; and
the one or more surfactants comprise an anionic, cationic, nonionic, or zwitterionic surfactant, or mixtures thereof.

17. A mesoporous material produced by a process of claim 1 .

18. The mesoporous material of claim 17 , wherein the process is a sol-gel micelle based process.

19. The mesoporous material of claim 17 , wherein micellization and inter-micellar interaction in said process are controlled by said one or more metal precursors, one or more surfactants, one or more interface modifiers, one or more lyotropic ion precursors, and optionally one or more organic and/or inorganic additives.

20. The mesoporous material of claim 17 , wherein the heating step comprises:
heating the micellar solution at a temperature and for a period of time sufficient to form a dried powder; and
heating the dried powder at a temperature and for a period of time sufficient to form the mesoporous material.

21. The mesoporous material of claim 17 , wherein the micellar solution is heated sequentially as follows:
at a temperature from about 75° C. to about 150° C. for a period from about 1 to about 12 hours; and
at a temperature from about 40° C. to about 80° C. for a period from about 1 to about 12 hours.

22. The mesoporous material of claim 17 , wherein the dried powder is heated sequentially as follows:
at a temperature from about 100° C. to about 200° C. for a period from about 2 to about 20 hours;
at a temperature from about 200° C. to about 300° C. for a period from about 1 to about 10 hours;
at a temperature from about 300° C. to about 400° C. for a period from about 1 to about 8 hours;
at a temperature from about 400° C. to about 500° C. for a period from about 0.5 to about 4 hours; and

Assignees

• Univ Connecticut

Inventors

• Suib Steven L
• Poyraz Altug Suleyman
• Jin Lei
• Kuo Chung-Hao

Classifications

• C01P2006/40

  Electric properties · CPC title

• C01G1/12

  Sulfides · CPC title

• B01J23/34

  Manganese · CPC title

• C01P2006/14

  Pore volume · CPC title

• B01J23/30

  Tungsten · CPC title