Composite materials containing organic polymer-encapsulated metal organic frameworks

Patent metadata

Field	Value
Publication number	US-11020724-B2
Application number	US-201615772385-A
Country	US
Kind code	B2
Filing date	Nov 10, 2016
Priority date	Nov 10, 2015
Publication date	Jun 1, 2021
Grant date	Jun 1, 2021

Abstract

Metal organic resins, composite materials composed of the metal organic resins, and anion exchange columns packed with the composite materials are provided. Also provided are methods of using the composite materials to remove metal anions from a sample, methods of using the metal organic resins as fluorescence sensors for detecting metal anions in a sample, and methods of making the metal organic resins and the composite materials. The metal organic resins are amine-functionalized metal organic frameworks and their associated counter anions. The composite materials are composed of metal organic resin particles coated with organic polymers, such as alginic acid polymers.

First claim

What is claimed is:

1. A composite material comprising:
metal organic resin particles comprising metal organic frameworks and associated counter anions, wherein the metal organic frameworks comprise metal nodes coordinated via organic molecular linkers to form a connected porous network and further wherein the organic molecular linkers are protonated and amine-functionalized; and
an organic polymer coating the metal organic resin particles.

2. The composite material of claim 1 , wherein the organic polymer is an alginic acid polymer.

3. The composite material of claim 1 , wherein the counter anions are halide anions.

4. The composite material of claim 3 , wherein the halide anions are chloride ions.

5. The composite material of claim 1 , wherein the metal nodes of the metal organic frameworks are Zr 6 nodes.

6. The composite material of claim 5 , wherein the metal organic resins have the formula: [Zr 6 O 4 (OH) 8 (H 2 O) 4 (H 2 PATP) 4 ]X − 6 , or the same formula, but with oxo ligands, aquo ligands, or a combination thereof in place of some or all of the hydroxo ligands, where H 2 PATP is 2-((pyridine-1-ium-2-ylmethyl)ammonio)terephthalate and X is a monovalent anion.

7. The composite material of claim 6 , wherein the organic polymer is an alginic acid polymer.

8. The composite material of claim 5 , wherein the metal organic resins have the formula: [Zr 6 O 4 (OH) 4 (NH 3 + -BDC) 6 ]X − 6 , or the same formula, but with oxo ligands, aquo ligands, or a combination thereof in place of some or all of the hydroxo ligands, where BDC is 1,4-benzenedicarboxylate and X is a monovalent anion.

9. The composite material of claim 8 , wherein the organic polymer is an alginic acid polymer.

10. An anion exchange column comprising:
a column; and
a mixture of an inert granular material and the composite material of claim 1 packed within the column.

11. The anion exchange column of claim 10 , wherein the mixture comprises no greater than 3 wt. % of the composite material.

12. The anion exchange column of claim 10 , wherein the inert granular material is sand.

13. A method of removing metal anions from a sample, the method comprising:
exposing a sample comprising metal anions to the composite material of claim 1 , whereby the metal anions undergo anion exchange with the counter anions of the composite material; and
separating the composite material from the sample.

14. A method of removing metal anions from a sample using the anion exchange column of claim 10 , the method comprising running a sample comprising metal anions through the anion exchange column, whereby the metal anions undergo anion exchange with the counter anions of the composite material.

15. The method of claim 14 , wherein the metal anions are chromium-containing anions, selenium-containing anions, or a combination thereof.

16. A method of making a composite material, the method comprising:
heating a mixture of a zirconium halide salt and NH 2 -H 2 BDC in an acidic aqueous solution, where NH 2 -H 2 BDC is 2-amino-terephthalic acid, whereby a reflux reaction between the zirconium halide salt and the NH 2 -H 2 BDC forms a suspension of metal organic resin particles in the solution, the metal organic resin comprising zirconium nodes coordinated via organic molecular linkers in a connected porous network, wherein the organic molecular linkers are protonated and amine-functionalized; and
adding an alkali metal alginate salt to the suspension, whereby the alkali metal alginate converts into alginic acid, which forms a water insoluble alginic acid polymer coating on, and flocculates, the metal organic resin particles.

17. A method of making a composite material, the method comprising:
forming an aqueous solution comprising an alkali metal alginate salt and metal organic resin particles, the metal organic resin particles comprising metal nodes coordinated via organic molecular linkers in a connected porous network, wherein the organic molecular linkers are protonated and amine-functionalized, whereby one or more monolayers of alginate-saturated water form a coating on the metal organic resin particles;
adding an alkali earth metal halide salt to the aqueous solution, whereby a water-insoluble coating of an alkali earth metal alginate forms around the metal organic resin particles;
removing the coated metal organic resin particles from the aqueous solution; and
reacting the coated metal organic resin particles with a hydrogen halide to protonate the amine-functionalized metal organic frameworks and convert the alkali earth metal alginate coating into an alginic acid polymer.

18. A method of making a composite material, the method comprising:
forming an aqueous solution comprising an alkali metal alginate salt and metal organic resin particles, the metal organic resin particles comprising metal nodes coordinated via organic molecular linkers in a connected porous network, wherein the organic molecular linkers are protonated and amine-functionalized, whereby one or more monolayers of alginate-saturated water form a coating on the metal organic resin particles; and
adding a hydrogen halide to the solution, whereby the hydrogen halide reacts with the alginate and the metal organic resin particles to protonate the amine-functionalized metal organic frameworks and to form an alginic acid polymer coating around the organic resin particles.

Assignees

• Univ Northwestern

Inventors

• Kanatzidis Mercouri G
• Sarma Debajit
• Manos Emmanouil

Classifications

• B01J47/02

  Column or bed processes · CPC title

• B01J47/018

  Granulation; Incorporation of ion-exchangers in a matrix; Mixing with inert materials · CPC title

• B01J41/08

  Use of material as anion exchangers; Treatment of material for improving the anion exchange properties · CPC title

• B01J20/3274

  Proteins, nucleic acids, polysaccharides, antibodies or antigens · CPC title

• B01J20/3206

  Organic carriers, supports or substrates · CPC title