Mesoporous metal oxides and processes for preparation thereof

Patent metadata

Field	Value
Publication number	US-9908103-B2
Application number	US-201314037100-A
Country	US
Kind code	B2
Filing date	Sep 25, 2013
Priority date	Sep 25, 2012
Publication date	Mar 6, 2018
Grant date	Mar 6, 2018

Abstract

A process for preparing a mesoporous metal oxide, i.e., transition metal oxide. Lanthanide metal oxide, a post-transition metal oxide and metalloid oxide. The process comprises providing an acidic mixture comprising a metal precursor, an interface modifier, a hydrotropic ion precursor, and a surfactant; and heating the acidic mixture at a temperature and for a period of time sufficient to form the mesoporous metal oxide. A mesoporous metal oxide prepared by the above process. A method of controlling nano-sized wall crystallinity and mesoporosity in mesoporous metal oxides. The method comprises providing an acidic mixture comprising a metal precursor, an interface modifier, a hydrotropic ion precursor, and a surfactant; and heating the acidic mixture at a temperature and for a period of time sufficient to control nano-sized wall crystallinity and mesoporosity in the mesoporous metal oxides. Mesoporous metal oxides and a method of tuning structural properties of mesoporous metal oxides.

First claim

What is claimed is:

1. A process for preparing a mesoporous metal oxide said process comprising:
providing an acidic inverse micellar mixture comprising a metal precursor, an interface modifier, a hydrotropic ion precursor, and a surfactant, wherein water is eliminated or minimized to prevent aggregation of metal oxide clusters; and
heating the acidic mixture at a temperature and for a period of time sufficient to form nano-sized wall crystallinity and mesoporosity in the mesoporous metal oxide,
wherein the mesoporous metal oxide has nano-sized wall crystallinity.

2. The process of claim 1 , wherein the heating step comprises:
heating the acidic mixture 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 nano-sized wall crystallinity and mesoporosity in the mesoporous metal oxide.

3. The process of claim 2 , wherein the acidic mixture 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.

4. The process of claim 2 , 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.

5. The process of claim 2 , 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.

6. The process of claim 2 , further comprising washing the dried powder with an alcohol for a period of time sufficient to remove organic components therefrom.

7. The process of claim 1 , wherein the metal precursor is selected from the group consisting of a transition metal precursor, a Lanthanide metal precursor, a post-transition metal precursor, a metalloid precursor, and mixtures thereof.

8. The process of claim 7 , wherein the transition metal precursor comprises a Group 3-12 transition metal precursor 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 precursor.

9. The process of claim 7 , wherein the Lanthanide metal precursor is selected from the group consisting of a La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu precursor.

10. The process of claim 7 , wherein the post-transition metal precursor is selected from the group consisting of an Al, Ga, In, Tl, Sn, Pb and Bi precursor.

11. The process of claim 7 , wherein the metalloid precursor is selected from the group consisting of a B, Si, Ge, As, Sb, Te, Po and At precursor.

12. The process of claim 1 , wherein the metal precursor is selected from the group consisting of metal nitrates, metal alkoxides, metal halides, metal phosphates, metal acetates, and M x O y oxides that are capable of dissolving in HNO 3 .

13. The process of claim 1 , wherein the metal precursor is selected from the group consisting of M(NO 3 ) x .yH 2 O (M=Mn, Fe, Co, Cu, Zn), tetraethyl orthosilicate (TEOS), tetramethyl orthosilicate (TMOS), titanium butoxide, zirconium n-propoxide, zirconium butoxide, Ce(NO 3 ) 3 .6H 2 O, Gd(NO 3 ) 3 .6H 2 O, and Sm(NO 3 ) 3 .6H 2 O.

14. The process of claim 1 , wherein the interface modifier comprises an aliphatic, alicyclic or aromatic hydrocarbon, oxygenated hydrocarbon or terpenoid hydrocarbon, of between about 1 and about 20 carbon atoms, or mixtures thereof, that allows the surfactant to organize itself into inverse micelles.

15. The process of claim 1 , wherein the hydrotropic ion precursor comprises HNO 3 , NaNO 3 , KNO 3 , metal halides, metal thiocyanides, or mixtures thereof.

16. The process of claim 1 , wherein the surfactant comprises an anionic, cationic, non-ionic, or zwitterionic surfactant, or mixtures thereof.

17. The process of claim 1 , wherein the surfactant comprises an EO/PO copolymer surfactant.

18. The process of claim 1 , wherein the surfactant comprises Pluronic® P65 (EO20PO30EO20), Pluronic® P85 (EO26PO40EO26), Pluronic® 25R4, Pluronic® F108 (EO129PO56EO129), Pluronic® P123 (EO20PO70EO20) or Pluronic® F127 (EO97PO69EO97).

19. The process of claim 1 , wherein the surfactant comprises a Triton® surfactant, a Tween® surfactant, glucose, or an AB or BC polymer surfactant, wherein A is polyisoprene butylene, B is styrene, and C is selected from glucose, amine, carboxyl group-containing compound, and polyethylene glycol (PEG).

20. The process of claim 1 , wherein the mesoporous metal oxide has a pore size (diameter) between about 1.5 nanometers and about 50 nanometers.

21. The process of claim 1 , which is conducted under process conditions sufficient to control pore size and pore size distribution of the metal oxide and crystal structure of nano-sized metal oxide walls.

22. The process of claim 1 , wherein the mesoporous metal oxide is selected from the group consisting of a transition metal oxide, a Lanthanide metal oxide, a post-transition metal oxide, a metalloid oxide, and mixtures thereof.

23. The process of claim 22 , wherein the transition metal oxide comprises a Group 3-12 transition metal oxide 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.

24. The process of claim 22 , wherein the Lanthanide metal oxide 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.

25. The process of claim 22 , wherein the post-transition metal oxide is selected from the group consisting of an Al, Ga, In, Tl, Sn, Pb and Bi oxide.

26. The process of claim 22 , wherein the metalloid oxide is selected from the group consisting of a B, Si, Ge, As, Sb, Te, Po and At oxide.

27. A method of controlling nano-sized wall crystallinity and mesoporosity in mesoporous metal oxides, said method comprising:
providing an acidic inverse micellar mixture comprising a metal precursor, an interface modifier, a hydrotropic ion precursor, and a surfactant, wherein water is eliminated or minimized to prevent the aggregation of metal oxide clusters; and
heating the acidic mixture at a temperature and for a period of time sufficient to control nano-sized wall crystallinity and mesoporosity in the mesoporous metal oxides;
wherein the mesoporous metal oxides have nano-sized wall crystallinity.

28. A method of tuning structural properties of crystalline mesoporous metal oxides, said method comprising:
providing an acidic sol-gel micellar mixture comprising a metal precursor, an interface modifier, a hydrotropic ion precursor, and a surfactant, wherein water is eliminat

Assignees

• Univ Connecticut

Inventors

• Suib Steven L
• Poyraz Altug Suleyman

Classifications

• C01B35/1027

  Oxides · CPC title

• C01P2002/72

  by d-values or two theta-values, e.g. as X-ray diagram · CPC title

• B82Y30/00

  Nanotechnology for materials or surface science, e.g. nanocomposites · CPC title

• B01J23/72

  Copper · CPC title

• C01B13/18

  by thermal decomposition of compounds, e.g. of salts or hydroxides · CPC title