Rapid metal organic framework molecule synthesis method

• US 20090131643A1
• Filed: 04/13/2007
• Published: 05/21/2009
• Est. Priority Date: 04/14/2006
• Status: Active Grant

• Current Assignee: Board of Trustees of The University of Illinois, University of Illinois
• Original Assignee: Board of Trustees of The University of Illinois
• Inventors: Ni, Zheng, Masel, Richard I.
• Granted Patent: US 7,880,026 B2
• Time in Patent Office: Days
• US Class Current: 534/16
• CPC Class Codes: C01G 9/00 Compounds of zinc
• CPC Class Codes: C01P 2002/72 by d-values or two theta-values, e.g. as X-ray diagram
• 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 2006/12 Surface area

Abstract

A rapid, simple and versatile metal organic framework molecule (MOF) synthesis method particularly adapted to make non-linear MOFs includes heating MOF precursors, such as a metal or metal oxide and an organic ligand, in a microwave oven for a period sufficient to achieve crystallization. Microwave-assisted MOF synthesis yields high quality MOF crystals in a reaction time ranging from about 5 seconds to about 2.5 minutes, compared to hours and days required in conventional solvothermal and hydrothermal methods. In addition, microwave assisted methods provide MOF materials with uniform crystal size and well-defined shape. Further, microwave synthesis of MOFs allows the size and shape of MOF crystals to be tailored for use in a wide range applications by manipulating reaction conditions. Secondary growth processes may also be employed to grow larger crystals using seeds obtained from microwave-assisted synthesis methods.

Claims

1. A method for synthesis of non-linear metal organic framework material, said method comprising steps of:

preparing a reactant solution including metal organic framework precursors; and

exposing the reactant solution to a microwave dose sufficient to induce crystallization of non-linear MOF material in the reactant solution.

2. The method of claim 1, wherein the microwave dose in said exposing step exceeds about 4 J/cm³.

3. The method of claim 1, wherein the microwave dose in said exposing step is applied for period of between about 5 seconds to about 2.5 minutes.

4. The method of claim 1, further comprising a step of post-processing growth of crystals in the metal organic framework material by one of a solvothermal or hydrothermal process that reaches and maintains a predetermined equilibrium temperature for a predetermined time.

5. The method of claim 1, wherein the metal organic framework precursors include a metal precursor and a corresponding spacer ligand in a predetermined ratio, and the amount of metal precursor is set to achieve a corresponding crystal size in the metal organic framework material.

6. The method of claim 1, wherein the non-linear metal organic framework material has a cubic structure.

7. The method of claim 1, wherein said preparing step includes mixing metal organic framework precursors in a solvent.

8. The method of claim 1, further comprising the step of removing metal organic framework material from the reactant solution after said step of exposing.

9. A process for making a selectively adsorbent MOF, Zn-MOF1, having a cubic crystalline structure with crystal sizes in the range from about 10 microns to about 30 microns, comprising (a) dissolving Zn(NO₃)₂*6H₂O, (0.18 g, 0.605 mmol) and 4,4′

,4″

,4′

″

-(21H,23H-porphine-5-10-15-20-tetrayl)tetrakis(benzoic acid), (0.199 g, 0.252 mmol), in 10 mL diethylformamide;

(b) sealing the dissolved solution, and (c) heating in a microwave oven.

10. The product made by the process of claim 9.

11. A process for making a selectively adsorbent MOF, Zn-MOF2, having a cubic crystalline structure with crystal sizes in the range from 2 to 4 microns, comprising (a) mixing Zn(NO₃)₂*6H₂O, (0.1 g, 0.336 mmol) and 2-anilino-5-bromoterephthalic acid, (2-anilino-5-BrBDCH₂) (0.0847 g, 0.252 mmol;

(b) dissolving the mixture in 10 mL diethylformamide;

(c) sealing the dissolved mixture; and

(d) heating in a microwave oven.

12. The product made by the process of claim 11.

13. A process for making a selectively adsorbent MOF, Zn-MOF3, having a cubic crystalline structure with crystals ranging from 4 to 7 microns, comprising (a) mixing Zn(NO₃)₂*6H₂O, (0.15 g, 0.504 mmol) with 2-trifluoromethoxy terephthalic acid, (2-trifluoromethoxy-BDCH₂) (0.0946 g, 0.378 mmol);

(b) dissolving the mixture in 10 mL diethylformamide, (c) sealing the dissolved mixture; and

(d) heating said dissolved mixture in a microwave oven.

14. The product made by the process of claim 13.

15. A process for making a selectively adsorbent MOF, Zn-MOF4, having crystals of irregular shape, comprising mixing Zn(NO₃)₂*6H₂O, (0.1 g, 0.336 mmol) with nitroterephthalic acid, (0.0532 g, 0.252 mmol);

(b) dissolving the mixture in 10 mL diethylformamide, sealing the dissolved mixture; and

(d) heating said dissolved mixture in a microwave oven.

16. The product made by the process of claim 15.

17. A process for making a selectively adsorbent MOF, Zn-MOF5, comprising (a) mixing Zn(NO₃)₂*6H₂O, (0.15 g, 0.504 mmol) with cis-cyclobutane-1,2-dicarboxylic acid (0.0545 g, 0.378 mmol);

(b) dissolving the mixture in 10 mL diethylformamide;

(c) sealing the dissolved mixture; and

(d) heating said dissolved mixture in a microwave oven.

18. The product made by the process of claim 17.

19. A process for making a selectively adsorbent MOF, Cu-MOF1, comprising (a) mixing Cu(NO₃)₂*2.5H₂O, (0.15 g, 0.645 mmol) with 2,5-thiophenedicarboxylic acid, (0.0833 g, 0.484 mmol);

(b) dissolving the mixture in 10 mL diethylformamide (c) sealing the dissolved mixture; and

(d) heating said dissolved mixture in a microwave oven.

20. The product made by the process of claim 19.

21. A process for making a selectively adsorbent MOF, CuMOF2, comprising (a) mixing Cu(NO₃)₂*2.5H₂O, (0.1 g, 0.430 mmol) with 2-(Trifluoromethoxy)terephthalic acid (2-trifluoromethoxy-BDCH₂) (0.0807 g, 0.322 mmol;

(b) dissolving the mixture in 10 mL diethylformamide;

(c) sealing the dissolved mixture; and

(d) heating said dissolved mixture in a microwave oven.

22. The product made by the process of claim 21.

23. A process for making a selectively adsorbent MOF, Tb-MOF1, having a rod-shaped crystalline structure, comprising mixing Tb(NO₃)₃*5H₂O, (0.1 g, 0.230 mmol), with Terephthalic acid (BDC) (0.0286 g, 0.172 mmol);

(b) dissolving the mixture in 10 mL diethylformamide;

(c) sealing the dissolved mixture; and

(d) heating said dissolved mixture in a microwave oven.

24. The product made by the process of claim 23.

25. A process for making a selectively adsorbent MOF, Tb-MOF2, comprising (a) mixing Tb(NO₃)₃*5H₂O, (0.1 g, 0.230 mmol), with 2,5-Thiophenedicarboxylic acid (0.0297 g, 0.172 mmol);

(b) dissolving the mixture in 10 mL diethylformamide;

(c) sealing the dissolved mixture; and

(d) heating said dissolved mixture in a microwave oven.

26. The product made by the process of claim 25.

27. A process for making a selectively adsorbent MOF, Cd-MOF1 comprising (a) mixing Cd(NO₃)₂*4H₂O, (0.1 g, 0.324 mmol), with cis-Cyclobutane-1,2-dicarboxylic acid (0.0350 g, 0.243 mmol);

(b) dissolving the mixture in 10 mL diethylformamide;

(c) sealing the dissolved mixture; and

(d) heating said dissolved mixture in a microwave oven.

28. The product made by the process of claim 27.

29. A process for making a selectively adsorbent MOF, Cd-MOF2, comprising (a) mixing Cd(NO₃)₂*4H₂O, (0.1 g, 0.324 mmol), with Nitroterephthalic acid (0.0456 g, 0.216 mmol);

(b) dissolving the mixture in 15 mL diethylformamide;

(c) sealing the dissolved mixture; and

(d) heating said dissolved mixture in a microwave oven.

30. The product made by the process of claim 29.

31. A process for making a selectively adsorbent MOF, Cd-MOF3, comprising (a) mixing Cd(NO₃)₂*4H₂O, (0.1 g, 0.324 mmol), with Terephthalic acid (0.0404 g, 0.243 mmol);

(b) dissolving the mixture in 10 mL diethylformamide;

(c) sealing the dissolved mixture; and

(d) heating said dissolved mixture in a microwave oven.

32. The product made by the process of claim 31.

33. A process for making a selectively adsorbent MOF, Co-MOF1, comprising (a) mixing Co(NO₃)₂*6H₂O, (0.1 g, 0.343 mmol), with Terephthalic acid (0.0428 g, 0.258 mmol;

(b) dissolving the mixture in 10 mL diethylformamide;

(c) sealing the dissolved mixture; and

(d) heating said dissolved mixture in a microwave oven.

34. The product made by the process of claim 33.

35. A process for making a selectively adsorbent MOF, Co-MOF2, comprising (a) mixing Co(NO₃)₂*6H₂O, (0.1 g, 0.343 mmol) with 1,3,5-benzenetricarboxylic acid (0.0542 g, 0.258 mmol);

(b) dissolving the mixture in 10 mL diethylformamide (c) sealing the mixture; and

(d) heating in a microwave oven.

36. The product made by the process of claim 35.

37. A process for making a selectively adsorbent MOF, Zn-MOF6, comprising mixing Zn(NO₃)₂*6H₂O, (0.05 g, 0.168 mmol) with 3,3-bis(trifluoromethyl)-1-oxo-5-isobenzofurancarboxylic acid (0.0396 g, 0.126 mmol);

(b) dissolving the mixture in 7 mL diethylformamide/3 mL H₂O;

(c) sealing the dissolved mixture; and

(d) heating the dissolved mixture in a microwave oven.

38. The product made by the process of claim 37.