Methods of making MOFs, systems for synthesizing MOFs, and methods of coating textiles with MOFs

Patent metadata

Field	Value
Publication number	US-12371444-B2
Application number	US-201917261248-A
Country	US
Kind code	B2
Filing date	Jul 19, 2019
Priority date	Jul 19, 2018
Publication date	Jul 29, 2025
Grant date	Jul 29, 2025

Abstract

A method of synthesis of metal organic frameworks (“MOFs”) includes preparing a metal solution by dissolving at least one metal salt in an aqueous solution and buffering the metal solution with a base to achieve a first pH, the metal solution optionally comprising an organic co-solvent, preparing a linker solution by adding at least one organic acid linker and at least one base to an aqueous solution, and mixing the metal solution and the linker solution to produce the MOFs. The at least one organic acid linker has an ability to be protonated or deprotonated in response to a second pH, and the mixture of the metal solution and the linker solution has a third pH value, where the third pH value is greater than a highest pK a of the organic acid linker. The MOFs may be applied to a textile.

First claim

The invention claimed is:

1. A method of synthesis of metal organic frameworks (“MOFs”), the method comprising:
preparing a metal solution by dissolving at least one metal salt in an aqueous solution and buffering the metal solution to achieve a first pH, the metal solution optionally comprising an organic co-solvent;
preparing a linker solution by adding at least one organic acid linker and at least one base to an aqueous solution, wherein the at least one organic acid linker has an ability to be protonated or deprotonated in response to a second pH; and
mixing the metal solution and the linker solution to produce the MOFs, wherein the mixture of the metal solution and the linker solution has a third pH value, the third pH value being from 0.1 to 3 pH units greater than a highest pK a of the organic acid linker, wherein the MOFs are produced in less than 1 minute after the mixing of the metal solution and the linker solution.

2. The method of claim 1 wherein the at least one metal salt is selected from the group consisting of ZrOCl 12 , ZrCl 4 , ZrBr 4 , ZrI 4 , ZrO(NO 3 ) 2 , Zr(ClO 4 ) 4 Zr(SO 4 ) 2 , Zr(PO 4 ) 4 ZrO(CH 3 COO) 2 , Zr(C 6 H 5 O 7 ) (“Zirconium citrate”), Zr(CH 2 C(CH 3 )CO 2 ) 4 (“Zirconium methacrylate”), Zr(CH 2 CHCO 2 ) 4 (“Zirconium acrylate”), Zr(OC 4 H 9 ) 4 (“Zirconium tertbutoxide”), Zr(OCH 2 CH 2 CH 3 ) 4 (“Zirconium (IV) propoxide”), Zr 6 O 4 (OH) 4 (CH 2 C(CH 3 )CO 2 ) 12 (“Zirconium (IV) oxo hydroxy methacrylate”), Cu(NO 3 ) 2 , CuCl, CuCl 2 , CuBr, CuBr 2 , CuI, CuI 2 , Cu(ClO 4 ) 2 , CuSO 4 , Cu 3 (PO 4 ) 2 Cu(CH 3 COO), Cu 3 (C 6 H 5 O 7 ) 2 (“Copper citrate”), Cu(CH 2 C(CH 3 )CO 2 ) 2 (“Copper methacrylate”), Cu(CH 2 CHCO 2 ) 2 (“Copper acrylate”), Cu((CH 3 ) 2 CHO) 2 (“Copper propoxide”), Zn(NO 3 ) 2 , ZnCl 2 , ZnBr 2 , ZnI 2 , Zn(ClO 4 ) 2 , ZnSO 4 , Zn 3 (PO 4 ) 2 , Zn(CH 3 COO), Zn 3 (C 6 H 5 O 7 ) 2 (“Zinc citrate”), Zn(CH 2 C(CH 3 )CO 2 ) 2 (“Zinc methacrylate”), Zn(CH 2 CHCO 2 ) 2 (“Zinc acrylate”), Zn(OCH 2 CH 2 CH 3 ) 2 (“Zinc propoxide”), AlCl 3 , AlBr 3 , AlI 3 , Al(NO 3 ) 3 , Al(ClO 4 ) 3 , Al 2 (SO 4 ) 3 , AlPO 4 , Al(CH 3 COO) 3 , Al(C 6 H 5 O 7 ) (“Aluminum citrate”), Al(CH 2 C(CH 3 )CO 2 ) 3 (“Aluminum methacrylate”), Al(CH 2 CHCO 2 ) 3 (“Aluminum acrylate”), Al((CH 3 ) 2 CHO) 3 (“Aluminum propoxide”), FeCl 2 , FeCl 3 , FeBr 3 , FeI 2 , Fe(NO 3 ) 2 , FeSO 4 , Fe 2 (SO 4 ) 3 , FePO 4 , Fe(ClO 4 ) 2 , Fe(CH 3 COO) 2 , Fe(C 6 H 5 O 7 ) (“Iron citrate”), Fe(CH 2 C(CH 3 )CO 2 ) 3 (“Iron methacrylate”), Fe(CH 2 CHCO 2 ) 3 (“Iron acrylate”), Fe((CH 3 ) 2 CHO) 3 (“Iron propoxide”), TiCl 2 , TiCl 3 , TiCl 4 , TiBr 4 , TiI 4 Ti(NO 3 ) 4 , Ti(ClO 4 ) 4 , Ti(SO 4 ) 2 , Ti 3 (PO 4 ) 4 , Ti(CH 3 COO) 4 , Ti(C 6 H 5 O 7 ) (“Titanium citrate”), Ti(CH 2 C(CH 3 )CO 2 ) 4 (“Titanium methacrylate”), Ti(CH 2 CHCO 2 ) 4 (“Titanium acrylate”), Ti((CH 3 ) 2 CHO) 4 (“Titanium propoxide”), MgCl 2 , MgBr 2 , MgI 2 , Mg(NO 3 ) 2 , Mg(SO 4 ), Mg(PO 4 ) 2 , Mg(ClO 4 ) 2 , Mg(CH 3 COO) 2 , Mg(C 6 H 5 O 7 ) (“Magnesium citrate”), Mg(CH 2 C(CH 3 )CO 2 ) 2 (“Magnesium methacrylate”), Mg(CH 2 CHCO 2 ) 2 (“Magnesium acrylate”), Mg((CH 3 ) 2 CHO) 2 (“Magnesium propoxide”), HfCl 4 , HfBr 4 , Hfl 4 , Hf(NO 3 ) 4 , Hf(SO 4 ) 2 , Hf 3 (PO 4 ) 4 , Hf(CH 3 COO) 4 , Hf(C 6 H 5 O 7 ) (“Hafnium citrate”), Hf(CH 2 C(CH 3 )CO 2 ) 4 (“Hafnium methacrylate”), Hf(CH 2 CHCO 2 ) 4 (“Hafnium acrylate”), Hf((CH 3 ) 2 CHO) 4 (“Hafnium propoxide”), CoCl 2 , CoCl 3 , CoBr 2 , CoI 2 , Co(NO 3 ) 2 , Co(ClO 4 ) 2 , Co(SO 4 ), Co(CH 3 COO), Co(CH 2 C(CH 3 )CO 2 ) 2 (“Cobalt methacrylate”), Co(CH 2 CHCO 2 ) 2 (“Cobalt acrylate”), and Co((CH 3 ) 2 CHO) 2 (“Cobalt propoxide”).

3. The method of claim 1 wherein the at least one organic acid linker is selected from the group consisting of a substituted or unsubstituted straight-chain or branched dicarboxylic acid having at least three carbon atoms and saturated and/or unsaturated C—C bonds, formula (I), formula (II), formula (III), and any combination thereof:

wherein
R1 and R2 are the same or different and are selected from the group consisting of hydrogen, amino, sulfo, hydroxo, carboxyl, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, phosphono, trifluoromethyl, trichloromethyl, and tribromomethyl.

4. The method of claim 1 wherein the at least one organic acid linker is selected from the group consisting of formula (IV), formula (V), and any combination thereof:

wherein
X1, X2, X3, X4, X5, and X6 are the same or different and are selected from the group consisting of C and N;
R1, R2, R3, R4, R5, and R6 are the same or different and are selected from the group consisting of hydrogen, amino, sulfo, hydroxo, carboxyl, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, phosphono, trifluoromethyl, trichloromethyl, tribromomethyl, 4-(carboxyphenol) benzyl, substituted or unsubstituted benzyl, and substituted or unsubstituted biphenyl; and
the at least one organic acid linker comprises at least two carboxyl groups.

5. The method of claim 1 wherein the organic acid linker is selected from the group consisting of terephthalic acid, 2-hydroxyterephthalic acid, 2,5-dihydroxyterephthalic acid, 2-aminoterephthalic acid, 2,5-diaminoterephthalic acid, 2-sulfoterephthalic acid, 2,5-disulfoterephthalic acid, 2-methylterephthalic acid, 2,5-methylterephthalic acid, 2-phosphonoterephtahlic acid, 2,5-diphosphonoterephthalic acid, cyclohexane-1,2,4,-tricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, cyclohexane-1,2,4,5-tetracarboxylic acid, fumaric acid, 1,4-naphthalenedicarboxylic acid, biphenyl-4,4′-dicarboxylic acid, 2-amino-4,4′-biphenyldicarboxylic acid, 2-sulfo-4,4′-biphenyldicarboxylic acid, trimesic acid, 1,3,5-cyclohexanetricarboxylic acid, 2-methylimidazole, benzimidazole, 1,3,5-benzenetrisulfonic acid, 1,4-benzenedisulfonic acid, tetraethyl 4,4′,4″,4′-(pyrene-1,3,6,8-tetrayl)tetrabenzoic acid.

6. The method of claim 1 wherein the organic acid linker is 2-aminoterephthalic acid.

7. The method of claim 1 wherein buffering the metal solution comprises adding ammonium acetate, sodium carbonate, sodium bicarbonate, dimethylamine, triethylamine, ammonium bicarbonate, disodium hydrogen phosphate, sodium chloride, sodium acetate, sodium citrate, sodium hydroxide, potassium hydroxide, potassium carbonate, potassium bicarbonate, calcium carbonate, calcium bicarbonate, or any combination thereof to the solution.

8. The method of claim 1 , wherein the first pH is from greater than zero to 7, the second pH is from 5.5 to 12.5, and the third pH is from 4.6 to 8.

9. The method of claim 1 further comprising heating the metal solution at a temperature, and subsequently allowing the metal solution to cool to room temperature.

10. The method of claim 1 further comprising adding a weak organic acid to the metal solution.

11. The method of claim 1 further comprising adding an acid to the metal solution, the acid selected from the group consisting of acetic acid, glycine, sulfuric acid, fluoroacetic acid, difluoroacetic acid, trifluoracetic acid, trichloroacetic acid, methacrylic acid, acrylic acid, propionic acid, and any combination thereof.

12. The method of claim 1 wherein the linker solution comprises a molar ratio of organic acid linker to base ranging from 1:30 to 1:0.5.

13. The method of claim 1 , wherein the MOFs are selected from the group consisting of UiO-66, UiO-66 (NH 2 ), UiO-67, UiO-66 (COOH), UiO-68, HKUST-1, ZI

Assignees

• Univ Virginia Patent Foundation

Inventors

• Giri Gaurav
• Huelsenbeck Luke

Classifications

• D06M13/50

  with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms · CPC title

• C07F3/06

  Zinc compounds · CPC title

• C07F1/08 Primary

  Copper compounds · CPC title

• D06M13/352

  having five-membered heterocyclic rings · CPC title

• D06M13/2035

  Aromatic acids · CPC title