Metal organic frameworks and methods of making and using same

Patent metadata

Field	Value
Publication number	US-11478774-B2
Application number	US-201716329561-A
Country	US
Kind code	B2
Filing date	Aug 29, 2017
Priority date	Aug 29, 2016
Publication date	Oct 25, 2022
Grant date	Oct 25, 2022

Abstract

Metal Organic Framework (MOF) materials and methods of making MOF materials. The methods include grinding of mixtures of metal hydroxide(s) and ligand(s). The MOF materials may have at least two different ligands. The MOF materials may have open metal sites. The MOF materials can be used in gas storage applications.

First claim

The invention claimed is:

1. A method of making metal organic frameworks (MOFs) comprising:
providing a starting material mixture comprising: an amorphous metal hydroxide or a coordination complex with oxo, hydroxo, and/or aquo ligands of a metal; and one or more ligand that does not comprise a solvent;
adding a polar protic solvent, polar aprotic solvent, or a combination thereof to the starting material mixture, and
grinding the starting material mixture to which the polar protic solvent, polar aprotic solvent, or combination thereof has been added, whereby MOFs are formed.

2. The method of claim 1 , wherein the starting material mixture comprises: the amorphous metal hydroxide or the coordination complex; and two of the ligands.

3. The method of claim 1 , wherein the MOFs are dried and/or extruded to form pellets.

4. The method of claim 1 , wherein the amorphous metal hydroxide is selected from the group consisting of amorphous chromium (III) hydroxide, amorphous Fe(III) hydroxide, amorphous copper(II) hydroxide, amorphous zirconium hydroxide, amorphous aluminum hydroxide, amorphous lanthanum (III) hydroxide, amorphous samarium (III) hydroxide, amorphous gadolinium (III) hydroxide, and combinations thereof, and/or wherein the metal of the coordination complex is selected from the group consisting of chromium (III), Fe(III), copper (II), zirconium (II), aluminum (III), lanthanum (III), samarium (III), gadolinium (III), and combinations thereof.

5. The method of claim 1 , wherein the ligand is selected from the group consisting of unsaturated polycarboxylic acids, branched polycarboxylic acids, polycyclic aromatic hydrocarbons with two or more carboxylic acid groups, polyheterocyclic aromatic hydrocarbons with two or more carboxylic acid groups, and combinations thereof.

6. The method of claim 1 , wherein the ligand is selected from the group consisting of unsaturated dicarboxylic acids, bi-, tri- and tetraphenyl polycarboxylic acids, naphthalenic dicarboxylic acids, and combinations thereof.

7. The method of claim 1 , wherein the ligand is selected from the group consisting of aryl or heteroaryl mono, di, or tricarboxylic acids, and combinations thereof.

8. The method of claim 1 , wherein the polar protic solvent is selected from the group consisting of ethanol, methanol, isopropanol, water, acetic acid, formic acid, and combinations thereof.

9. The method of claim 1 , wherein the polar aprotic solvent is selected from the group consisting of ethyl acetate, tetrahydrofuran, N-methylpyrrolidone, acetone, acetonitrile, dimethyl sulfoxide, dimethylformamide, and combinations thereof.

10. The method of claim 1 , wherein the amorphous metal hydroxide:ligand(s) ratio or the coordination complex:ligand(s) ratio is a stoichiometric ratio.

11. The method of claim 1 , wherein there is no free solvent in the reaction mixture after reaction.

12. A crystalline MOF material having one or more metal ion, two or more ligands, and a porous bulk morphology comprising a plurality of interconnected pores, wherein the two or more ligands are different and the crystalline MOF material has at least 5% more open metal sites than a MOF material having the same metal(s) and the same metal oxidation state(s) and only one of the two or more ligands.

13. The crystalline MOF material of claim 12 , wherein at least one of the one or more metal ion has an open metal site free of coordination with the two or more ligands.

14. The crystalline MOF material of claim 12 , wherein the one or more metal ion is selected from the group consisting of chromium (III), iron (III), copper(II), zirconium(II), aluminum (III), lanthanum (III), samarium (III), gadolinium (III), and combinations thereof.

15. The crystalline MOF material of claim 12 , wherein the two or more ligands are selected from the group consisting of aryl or heteroaryl mono-, di-, or tricarboxylic acids, and combinations thereof.

16. The crystalline MOF material of claim 15 , wherein the two or more ligands are selected from the group consisting of benzene dicarboxylic acids, benzene tricarboxylic acids, pyridine carboxylic acids, and combinations thereof.

17. The crystalline MOF material of claim 16 , wherein the two or more ligands are selected from the group consisting of 1,3-benzenedicarboxylic acid, 1,4-benzenedicarboxylic acid, 1,3,5-benzenetricarboxylic acid, isonicotinic acid, and combinations thereof.

18. The crystalline MOF material of claim 12 , wherein the crystalline MOF material has 5% to 66% more open metal sites than a MOF material having the same metal(s) and the same metal oxidation state(s) and only one of the two or more ligands.

19. A method of gas storage comprising use of a MOF material of claim 12 .

20. The method of claim 19 , wherein the MOF material is pelletized.

21. The method of claim 1 , the method further comprising preparing or precipitating the amorphous metal hydroxide or the metal coordination complex, prior to providing a starting material mixture.

22. The method of claim 1 , wherein the starting material mixture comprises the amorphous metal hydroxide or the coordination complex in the form of a colloidal gel.

23. The method of claim 1 , wherein the MOFs comprise two or more different ligands and have at least 5% more open metal sites than MOF materials having the same metal(s) and same metal oxidation state(s) and only one of the two or more different ligands.

24. The method of claim 1 , wherein the MOFs comprise two or more different ligands and have 5% to 66% more open metal sites than MOF materials having the same metal(s) and same metal oxidation state(s) and only one of the two or more different ligands.

25. The crystalline MOF material of claim 18 , wherein the pores have a diameter or longest dimension perpendicular to the long axis of the pore of 20 nm to 200 nm.

26. The crystalline MOF material of claim 12 , wherein the two or more ligands consist of a first ligand and a second ligand and wherein the second ligand is 5-35% of the total ligands.

27. A method of making metal organic frameworks (MOFs) comprising:
providing a starting material mixture comprising a metal hydroxide and two or more ligands wherein the two or more ligands are different,
adding a polar protic solvent, polar aprotic solvent, or a combination thereof to the starting material mixture,
grinding the starting material mixture to which the polar protic solvent, polar aprotic solvent, or combination thereof has been added, and
forming MOFs having at least 5% more open metal sites than a MOF material having the same metal(s) and same metal oxidation state(s) and only one of the two or more ligands.

Assignees

• Univ Cornell

Inventors

• Hinestroza Juan Paulo
• Kim Manuela Leticia
• Otal Eugenio Hernan

Classifications

• F17C11/007

  for hydrocarbon gases, such as methane or natural gas, propane, butane or mixtures thereof [LPG] · CPC title

• B01J20/3007

  Moulding, shaping or extruding · CPC title

• B01J20/28083

  being in the range 2-50 nm, i.e. mesopores · CPC title

• B01J20/3085

  Chemical treatments not covered by groups B01J20/3007 - B01J20/3078 · CPC title

• B01J20/28085

  being more than 50 nm, i.e. macropores · CPC title