IP Library Granted Patent US 8,501,068
Granted Patent B2
US 8,501,068 · App. 12/741,178 · Granted Aug 6, 2013

Layered zeolite materials and methods related thereto

Inventors: Michael Tsapatsis (Minneapolis, MN); Sudeep Maheshwari (Cambridge, MA); Frank S. Bates (St. Louis Park, MN); William J. Koros (Atlanta, GA)
Assignees: Regents of the University of Minnesota; Georgia Institute of Technology
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 8,501,068
App. No.
12/741,178
Granted
Aug 6, 2013
Kind
B2
Abstract

A novel oxide material (MIN-I) comprising YO 2 ; and X 2 O 3 , wherein Y is a tetravalent element and X is a trivalent element, wherein X/Y=O or Y/X=30 to 100 is provided. Surprisingly, MIN-I can be reversibly deswollen. MIN-I can further be combined with a polymer to produce a nanocomposite, depolymerized to produce predominantly fully exfoliated layers (MIN-2), and pillared to produce a pillared oxide material (MIN-3), analogous to MCM-36. The materials are useful in a wide range of applications, such as catalysts, thin films, membranes, and coatings.

Claims (116)

1. A method comprising reversibly swelling an oxide material to produce an unwashed swollen layered oxide material, the oxide material having a first layer structure; and

washing the unwashed swollen layered oxide material with water to produce a washed swollen layered oxide material having a second layer structure substantially the same as the first layer structure and an X-ray diffraction pattern comprising:

d(Å)

100 I/I 0

40.7 ± 1.8 

vs

 20 ± 0.38

w

13.4 ± 0.17 

w

12.3 ± 0.14 

w

10.45 ± 0.1  

w

9.3 ± 0.08

w

6.7 ± 0.04

w

4.4 ± 0.03

w

3.9 ± 0.03

w

3.5 ± 0.03

w

3.4 ± 0.03

w

3.3 ± 0.03

w,

wherein d(Å)=interplanar spacing;

I=peak height intensity;

I 0 =intensity of strongest peak:,

100 I/I 0 =relative peak intensity;

vs=greater than 60 up to about 100; and

w=zero up to about 20; and wherein the oxide material is a layered oxide material which is swollen at room temperature.

2. The method of claim 1 wherein the second layer structure is the same as the first layer structure.

3. The method of claim 1 further comprising unswelling the washed swollen layered oxide material to produce the oxide material.

4. The method of claim 1 further comprising pillaring the washed swollen layered oxide material to produce a pillared layered oxide material having an X-ray diffraction pattern comprising:

d(Å)

100 I/I 0

43.9 ± 1.9 

vs

20.6 ± 0.4 

w

15.1 ± 0.21 

w

12.2 ± 0.14 

w

10.7 ± 0.14 

w

9.2 ± 0.14

w

6.9 ± 0.05

w

6.1 ± 0.04

w

4.4 ± 0.03

w

3.9 ± 0.03

w

3.5 ± 0.03

w

3.4 ± 0.03

w

3.3 ± 0.03

w,

wherein the oxide material is a pillared oxide catalyst and

d(Å)=interplanar spacing;

I=peak height intensity;

I 0 =intensity of strongest peak;

100 I/I 0 =relative peak intensity;

vs=greater than 60 up to about 100; and

w=zero up to about 20.

5. The method of claim 1 further comprising combining the washed swollen layered oxide material with a polymer to produce a composite.

6. The method of claim 5 wherein the composite is made with solvent casting and the polymer is a polystyrene, polypropylene, polyolefin, polymethacrylate, polyvinylalcohol, polyacrylamide, polycaprolactone, a copolymer of ethylene, a copolymer of propylene, a copolymer of acetate, poly(ethylene terephthalate), nylon, polysulfone, polyimide, polyamidimide, polybenzaimidazole, or any combination thereof.

7. The method of claim 4 wherein the composite is made with melt extrusion and the polymer is a polystyrene, polypropylene, polyolefin, polymethacrylate, polyvinylalcohol, polyacrylamide, polycaprolactone, a copolymer of ethylene, a copolymer of propylene, a copolymer of acetate, poly(ethylene terephthalate), nylon or any combination thereof.

8. The method of claim 7 further comprising removing the polymer from the composite to produce an exfoliated layered oxide material having an X-ray diffraction pattern comprising:

d(Å)

100 I/I 0

20.06 ± 1.35 

w-m

12.20 ± 0.13 

vs

10.93 ± 0.16 

s

8.76 ± 0.09

s

6.80 ± 0.05

w

6.04 ± 0.04

m-s

5.52 ± 0.03

w

4.37 ± 0.03

w

3.89 ± 0.02

m-s

3.74 ± 0.02

w-m

3.51 ± 0.04

w

3.41 ± 0.01

vs-m

3.28 ± 0.01

w

3.17 ± 0.01

w,

wherein d(Å)=interplanar spacing;

I=peak height intensity;

I 0 =intensity of strongest peak;

100 I/I 0 =relative peak intensity;

vs=greater than 60 up to about 100;

s=greater than 40 up to about 60;

m=greater than 20 up to 40; and

w=zero up to about 20.

9. The method of claim 8 wherein the polymer is removed by depolymerizing the composite with calcination or by dissolving the composite in a solvent to produce exfoliated layers and separating the exfoliated layers.

10. The method of claim 8 further comprising forming a film or a coating on a support.

Assignments (4)
CONFIRMATORY LICENSE Recorded Nov 7, 2012
From: REGENTS OF THE UNIVERSITY OF MINNESOTA
To: ENERGY, UNITED STATES DEPARTMENT OF
Reel/Frame 029286/0005 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 3, 2010
From: KOROS, WILLIAM J.
To: GEORGIA INSTITUTE OF TECHNOLOGY
Reel/Frame 025382/0072 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 3, 2010
From: KOROS, WILLIAM J.
To: GEORGIA INSTITUTE OF TECHNOLOGY
Reel/Frame 025382/0084 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 3, 2010
From: TSAPATSIS, MICHAEL; MAHESHWARI, SUDEEP; BATES, FRANK S.
To: REGENTS OF THE UNIVERSITY OF MINNESOTA
Reel/Frame 025382/0098 →
Continuity (2)
Provisional Application 60985551 · Nov 5, 2007
Related Publication 20110040013A1 · Feb 17, 2011