Method for preparing, in situ, metal-organic framework by using control of diffusion within ionic polymer

Patent metadata

Field	Value
Publication number	US-11697104-B2
Application number	US-201816954142-A
Country	US
Kind code	B2
Filing date	Dec 28, 2018
Priority date	Jan 2, 2018
Publication date	Jul 11, 2023
Grant date	Jul 11, 2023

Abstract

Disclosed is a method for preparing a matrix containing metal-organic frameworks (MOFs), comprising the steps of: 1) mixing an organic ligand precursor solution and an anionic polymer-containing solution to produce a mixed solution; and 2) adding a metal salt to the mixture solution. In addition, the present disclosure provides a matrix containing MOFs prepared according to the preparation method, and an adsorbent comprising the same. Furthermore, a method for performing fluid separation by using a matrix containing MOFs prepared according to the preparation method is disclosed.

First claim

The invention claimed is:

1. A method for preparing a matrix containing metal-organic frameworks (MOFs), the method comprising steps of:
1) mixing a liquid organic ligand precursor solution and a liquid anionic polymer-containing solution to produce a mixed solution, the organic ligand precursor and the anionic polymer being dissolved in the mixed solution; and
2) adding a metal salt to the mixed solution to form the MOFs in the matrix,
wherein the MOFs are uniformly dispersed in the matrix; and
wherein the MOFs and the polymer in the matrix are adhered to each other.

2. The method of claim 1 , wherein step 1) further comprises step 1-1) of adding a crosslinkable metal salt to the mixed solution, forming at least one solid, the at least one solid being the matrix throughout.

3. The method of claim 2 , wherein adding the crosslinkable metal salt forms at least one solid with the anionic polymer and the organic ligand, the at least one solid being the matrix throughout.

4. The method of claim 1 , further comprising, before step 1):
step 1-0) of mixing the anionic polymer and a flexible polymer to produce an anionic polymer-containing solution.

5. The method of claim 1 , wherein the MOFs have windows formed inside the MOFs wherein the windows have a uniform window size.

6. The method of claim 1 , wherein the matrix comprises 10 to 50% by weight (wt %) of MOFs based on a total weight of the matrix.

7. The method of claim 1 , wherein the anionic polymer is at least one selected from the group consisting of alginate, carboxymethyl cellulose, hyaluronic acid, poly(acrylic acid) (PA) and its derivatives, poly(methyl acrylate) (PMA) and its derivatives, poly(thiophene acetic acid) and its derivatives, poly(sulfonate styrene) (PSS) and its derivatives, and a combination thereof.

8. The method of claim 7 , wherein the anionic polymer is alginate.

9. The method of claim 1 , wherein the anionic polymer is a substitute polymer having anionic properties.

10. The method of claim 9 , wherein the substitute polymer is an anionic cellulose microfiber.

11. The method of claim 1 , wherein the metal salt of step 2) is derived from at least one metal selected from the group consisting of copper (Cu), zinc (Zn), iron (Fe), nickel (Ni), zirconium (Zr), chromium (Cr), scandium (Sc), cobalt (Co), titanium (Ti), manganese (Mn), vanadium (V), aluminum (Al), magnesium (Mg), gallium (Ga), indium (In), yttrium (Y), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag) and cadmium (Cd).

12. The method of claim 1 , wherein the organic ligand precursor solution comprises a weak basic material having a pK b value of 3 to 6.

13. A matrix containing metal-organic frameworks (MOFs), prepared by the method of claim 1 ,
wherein the MOFs are uniformly dispersed in the matrix; and
wherein the MOFs and the polymer in the matrix are adhered to each other.

14. An adsorbent comprising the matrix containing MOFs of claim 13 .

15. A method for separating first fluid having a first single molecule size V1 or second fluid having a second single molecule size V2 from a fluid mixture comprising the first fluid and the second fluid (provided that V1≠V2), the method comprising the step of:
passing the fluid mixture through the matrix containing metal-organic frameworks (MOFs) prepared by the method of claim 13 ,
wherein the MOFs have adsorption property or a window size that allows the first fluid to pass and does not allow the second fluid to pass therethrough.

Assignees

• Daegu Gyeongbuk Inst Science & Tech

Inventors

• Jeong Nak Cheon
• Lim Jeong Ho
• Lee Eun Ji

Classifications

• B01J20/267

  Cross-linked polymers · CPC title

• B01J20/226 Primary

  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 title

• C07F1/08

  Copper compounds · CPC title

• B01D15/08 Primary

  Selective adsorption, e.g. chromatography · CPC title

• B01J20/3085

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