High gain selective metal organic framework preconcentrators

• US 8,123,834 B2
• Filed: 10/06/2006
• Issued: 02/28/2012
• Est. Priority Date: 10/06/2005
• Status: Active Grant

• Current Assignee: Board of Trustees of The University of Illinois
• Original Assignee: Board of Trustees of The University of Illinois
• Inventors: Masel, Richard I., Ni, Zheng, Shannon, Mark A.
• Primary Examiner(s): CLEMENTE, ROBERT ARTHUR
• Application Number:
  US11/539,405
• Publication Number:
  US 20100132547A1
• Time in Patent Office: 1,971 Days
• Field of Search: 95/85, 95/88, 95/89, 95/90, 951/41, 961/05, 961/08, 961/54, 73/233.9, 73/234.1, 73/234.2, 4235921-643
• US Class Current: 95/90
• CPC Class Codes: B01D 15/00 Separating processes involving the treatment of liquids with solid sorbents using liquid sorbents B01D11/00; ion exchange processes or materials, sorbent materials in general B01J, e.g. sorbents for chromatography B01J20/281; for investigating or analysing materials G01N30/00; Apparatus therefor
• CPC Class Codes: B01D 2253/204 Metal organic frameworks (MOF's)
• CPC Class Codes: B01D 2257/70 Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
• CPC Class Codes: B01D 2259/4583 for removing chemical, biological and nuclear warfare agents
• CPC Class Codes: B01J 20/22 comprising organic material
• CPC Class Codes: B01J 20/226 Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF] preparation of metal complexes containing carboxylic acid moieties C07C51/418; MOF's per se C07F
• CPC Class Codes: B01J 20/3265 with an organic functional group containing a metal, e.g. a metal affinity ligand
• CPC Class Codes: B01J 2220/54 Sorbents specially adapted for analytical or investigative chromatography
• CPC Class Codes: G01N 1/405 by adsorption or absorption
• CPC Class Codes: G01N 2001/028 Sampling from a surface, swabbing, vaporising

Abstract

Novel metal organic framework (MOF) molecules and methods of synthesizing them are described. MOFs are organometallic crystalline structures that have high sorption capacity due to high surface area, tailorable selectivity, an inert nature, and thermal stability at high temperatures. MOFs may be used as sorbents in preconcentrators for analytical devices to provide orders of magnitude of improved sensitivity in analyte detection. MOFs are also useful as sorbents in new compact and portable micropreconcentrator designs such as a modified purge and trap system and a multi-valve microelectromechanical system (MEMS) to achieve high gain in analyte detection. Further, MOFs may be used as coatings for novel microstructure arrays in micropreconcentrators where the microstructures are designed to increase the surface area to volume ratio inside the micropreconcentrator while minimizing the pressure drop across the micropreconcentrator.

Claims

1. A method of using a metal organic framework (“

MOF”

) as a sorbent of an analyte in a preconcentrator or micropreconcentrator having a microelectromechanical (“

MEMS”

) valve system with at least three (3) valves in the preconcentrator or micropreconcentrator, said method comprising the steps of;

a) concentrating an analyte by sorbing it on a MOF highly selective to the analyte;

b) desorbing the analyte from the MOF; and

c) conducting the desorbed analyte to a device for analysis.

2. The method of claim 1, wherein one of the preconcentrator or micropreconcentrator is a purge and trap system, personal respirator, array of microstructures, dosimeter, disc, pellet, or swab.

3. The method of claim 1, wherein the MEMS valve system has 4 or 5 valves.

4. The method of claim 1, wherein the MOF has a thermal stability of up to about 300°

C. to about 400°

C.

5. The method of claim 1, wherein the MOF sorbs substantially all of the analyte.

6. The method of claim 1, wherein after sorbing the analyte, the MOF releases the analyte.

7. The method of claim 6, wherein the MOF releases the analyte by thermal desorption.

8. The method of claim 1, wherein the MOF comprises particles or a film.

9. The method of claim 8, wherein the MOF particles have a diameter of between about 20 nanometers to about 500 microns.

10. The method of claim 9, wherein the MOF particles have a diameter of between about 100 nanometers to about 50 microns.

11. The method of claim 1, wherein the MOF comprises one or more materials selected from the group consisting of Zn-MOF1, Zn-MOF2, Zn-MOF3, Zn-MOF4, Zn-MOF5, Cu-MOF1, Cu-MOF2, Tb-MOF1, Tb-MOF2, Cd-MOF1, Cd-MOF2, Cd-MOF3, CoMOF1, Co-MOF2, Zn-MOF6, MOF-5, Cu(4,4′

-bpy)_1.5NO₃(H₂O)_1.25, IRMOF2, [Cu₃(TMA)₂]_n, [Cu(OH)—

(C₅H₄NCO₂)], MOF-38, Ag(4,4′

-bpy)NO₃, IRMOF3 and IRMOF7.

12. The method of claim 1, wherein the MOF is selective to a predetermined analyte or group of analytes.

13. The method of claim 1, wherein the MOF sorbs analytes selected from the group consisting of explosives and chemical warfare agents.

14. The method of claim 1, wherein the MOF sorbs analytes selected from the group consisting of XV, sarin, DMMP, PMP, diethyl methylphosphonate (DEMP), diisopropyl methylphophonate (DIMP), dichlorohexane, malathion, acetic anhydride, TNT, and RDX.

15. A system for collecting an analyte from a sample comprising a preconcentrator or micropreconcentrator including:

a) an inlet to receive the sample;

b) a collection chamber containing a sorbent comprising a metal organic framework (“

MOF”

); and

c) a microelectromechanical (“

MEMS”

) valve system in the preconcentrator or micropreconcentrator having at least three (3) valves to control the flow of the sample through the system.

16. The system of claim 15, wherein said MEMS valve system has 4 or 5 valves.

17. The system of claim 15, wherein the MEMS valve system can be positioned in at least a first position, a second position, and a third position, wherein:

when the MEMS valve system is positioned in the first position, the collection chamber containing the MOF is exposed to a carrier gas optionally comprising an analyte,

when the MEMS valve system is positioned in the second position, the collection chamber containing the MOF is coupled to a means for desorption of analyte present on the MOF, and

when the MEMS valve system is positioned in the third position, the collection chamber containing the MOF can be exposed to a purge gas.

18. The system of claim 15, wherein the MOF has a thermal stability of up to about 300°

C. to about 400°

C.

19. The system of claim 15, wherein the MOF comprises particles or a film.

20. The system of claim 15, wherein the MOF particles have a diameter of between about 20 nanometers to about 500 microns.

21. The system of claim 20, wherein the MOF particles have a diameter of between about 100 nanometers to about 50 microns.

22. The system of claim 15, wherein the MOF comprises one or more materials selected from the group consisting of Zn-MOF1, Zn-MOF2, Zn-MOF3, Zn-MOF4, Zn-MOF5, Cu-MOF1, Cu-MOF2, Tb-MOF1, Tb-MOF2, Cd-MOF1, Cd-MOF2, Cd-MOF3, CoMOF1, Co-MOF2, Zn-MOF6, MOF-5, Cu(4,4′

-bpy)_1.5NO₃(H₂O)_1.25, IRMOF2, [Cu₃(TMA)₂]_n, [Cu(OH)—

(C₅H₄NCO₂)], MOF-38, Ag(4,4′

-bpy)NO₃, IRMOF3 and IRMOF7.

23. The system of claim 15, wherein the MOF sorbs analytes selected from the group consisting of explosives and chemical warfare agents.

24. The system of claim 15, wherein the MOF sorbs analytes selected from the group consisting of XV, sarin, DMMP, PMP, diethyl methylphosphonate (DEMP), diisopropyl methylphophonate (DIMP), dichlorohexane, malathion, acetic anhydride, TNT, and RDX.