Metal organic framework (MOF) structured object and method

Patent metadata

Field	Value
Publication number	US-10751694-B2
Application number	US-201815880976-A
Country	US
Kind code	B2
Filing date	Jan 26, 2018
Priority date	Jan 26, 2018
Publication date	Aug 25, 2020
Grant date	Aug 25, 2020

Abstract

A method of making a metal organic framework (MOF)-polymer composite material includes forming a homogeneous solution comprising a solvent, a metal salt, a polymer which is soluble in the solvent, and a reactant which can be synthesized to provide an organic linker during formation of a MOF structure, synthesizing the homogeneous solution to crystallize a MOF structure in the homogenous solution to yield the MOF structure distributed in a remainder solution, applying an antisolvent to the remainder solution with the MOF structure distributed in the remainder solution to form a polymer-rich phase, where the MOF structure is integrated into the polymer matrix during forming of the polymer matrix to produce a MOF-polymer composite material. The MOF-polymer composite material can be formed on a substrate to produce a MOF structured object, which can be a membrane, film, or other object.

First claim

What is claimed is:

1. A method of making a metal organic framework (MOF)-polymer composite material, the method comprising:
forming a homogeneous solution by combining a MOF liquor and a polymer solution;
wherein the MOF liquor includes a first solvent, a metal salt, and a reactant;
wherein the reactant provides an organic linker during formation of a MOF structure;
synthesizing, via crystallization of the homogeneous solution, the MOF structure in the homogenous solution;
wherein the crystallization of the MOF structure in the homogeneous solution yields the MOF structure distributed in a remainder solution; and
demixing the remainder solution to form a polymer-rich phase;
wherein the MOF structure is surrounded by the polymer-rich phase to produce a MOF-polymer composite material.

2. The method of claim 1 , wherein:
the polymer solution comprises a solvent and a polymer;
the polymer is soluble in the solvent;
demixing the remainder solution includes applying an antisolvent to the remainder solution with the MOF structure distributed in the remainder solution, to form the polymer-rich phase;
the polymer is not soluble in the antisolvent; and
the MOF structure is not soluble in the antisolvent.

3. The method of claim 2 , wherein the antisolvent comprises water.

4. The method of claim 2 , wherein the solvent comprises dimethylformamide (DMF).

5. The method of claim 2 , wherein the polymer comprises polyvinylidene difluoride (PVDF).

6. The method of claim 2 , wherein the polymer is selected from a group consisting of: poly(hexamethylenevinylene), polyoctenamer, polysulfone, poly(4-vinylphenol), PVDF rubber, poly(perfluorocyclobutane), polyvinylpyridine, carboxymethylcellulose, poly(vinylbenzyl alcohol), polystyrene, and mixtures thereof.

7. The method of claim 1 , further comprising:
distributing the homogenous solution on a substrate prior to crystallization of the MOF structure; and
separating the MOF-polymer composite material from the substrate to provide a MOF structured object.

8. The method of claim 7 , wherein the MOF structured object is one of a film and a membrane.

9. The method of claim 7 , wherein the substrate defines a net shape of the MOF structured object.

10. The method of claim 1 , wherein:
the MOF structure is characterized by a pore size distribution; and
the pore size distribution of the MOF structure distributed in the remainder solution is substantially unchanged after demixing to form the polymer-rich phase.

11. The method of claim 1 , wherein the MOF structure is homogeneously distributed in the polymer-rich phase such that the MOF-polymer composite material is a homogeneous composite material.

12. The method of claim 1 , further comprising:
controlling the crystallization of the MOF structure in the homogeneous solution such that the MOF structure is uniform in at least one of crystal size, pore size, and morphology.

13. The method of claim 12 , wherein controlling the crystallization of the MOF structure further comprises:
controlling at least one of a crystallizing time and a crystallizing temperature.

14. The method of claim 1 , wherein:
the polymer solution comprises a solvent and a polymer;
the polymer is soluble in the solvent; and
during demixing, the polymer inverts from a solvent phase to form the polymer-rich phase.

15. The method of claim 14 , wherein the polymer comprises at least one of a crystalline polymer and an amorphous polymer such that during demixing, the polymer-rich phase inverts by at least one of recrystallization and gelation.

16. The method of claim 1 , wherein
the polymer solution comprises:
a second solvent, and a polymer; and
wherein the polymer is soluble in the second solvent.

17. The method of claim 16 , wherein the reactant comprises benzene-1,3,5-tricarboxylic acid (H3BTC).

18. A method of making a metal organic framework (MOF)-polymer composite material, the method comprising:
forming a homogeneous solution comprising:
a solvent, a metal salt, a reactant, and a polymer;
wherein the reactant provides an organic linker during formation of a MOF structure; and
wherein the polymer is soluble in the solvent;

synthesizing the homogeneous solution to crystallize the MOF structure in the homogenous solution;
wherein crystallizing the MOF structure in the homogeneous solution yields the MOF structure distributed in a remainder solution;
applying an antisolvent to the remainder solution with the MOF structure distributed in the remainder solution, to form a polymer-rich phase;
wherein:
the polymer is not soluble in the antisolvent; and
the MOF structure is not soluble in the antisolvent; and

wherein the MOF structure is integrated into the polymer-rich phase during forming of the polymer-rich phase to produce a MOF-polymer composite material.

19. The method of claim 18 , further comprising:
distributing the homogenous solution on a substrate prior to crystallization of the MOF structure; and
separating the MOF-polymer composite material from the substrate to provide a MOF structured object;
wherein the MOF structured object is one of a film and a membrane.

20. A metal organic framework (MOF)-polymer composite material prepared by a process comprising the steps of:
forming a homogeneous solution by combining a MOF liquor and a polymer solution;
wherein the MOF liquor includes a first solvent, a metal salt, and a reactant;
wherein the reactant provides an organic linker during formation of a MOF structure;
synthesizing, via crystallization of the homogeneous solution, the MOF structure in the homogenous solution;
wherein the crystallization of the MOF structure in the homogeneous solution yields the MOF structure distributed in a remainder solution;
demixing the remainder solution to form a polymer-rich phase;
wherein the MOF structure is surrounded by the polymer-rich phase to produce a MOF-polymer composite material;
wherein the polymer-rich phase is configured as one of a membrane and a film formed of the MOF-polymer composite material; and
wherein the MOF structure distributed in the remainder solution and in the one of the membrane and film formed of the MOF-polymer composite material is characterized by one of:
substantially the same pore size distribution; and
substantially the same crystal size distribution; and wherein the pore size distribution of the MOF structure is within a range of from 5 to 9 Angstroms.

Assignees

• Gm Global Tech Operations Llc

Inventors

• Dailly Anne M
• Dai Fang
• Fuller Timothy J

Classifications

• H01M50/406

  Moulding; Embossing; Cutting · CPC title

• B01J35/70

  characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00) · CPC title

• B01D67/00793

  Dispersing a component, e.g. as particles or powder, in another component · CPC title

• B01D69/1411

  containing dispersed material in a continuous matrix · CPC title

• B01D71/028

  Molecular sieves (carbon B01D71/021) · CPC title