CRYSTAL STRUCTURE-MODULATED ZEOLITIC IMIDAZOLATE FRAMEWORK NANOPARTICLES AND METHOD OF PRODUCING THE SAME

• US 20200131214A1
• Filed: 10/22/2019
• Published: 04/30/2020
• Est. Priority Date: 10/24/2018
• Status: Active Grant

• Current Assignee: Sogang University Research & Business Development Foundation
• Original Assignee: Sogang University Research & Business Development Foundation
• Inventors: Lee, Jong Suk, Cho, Kie Yong, Lee, Jin Won, Oh, Byung Keun, Na, Jeong Geol, An, He Seong, Shin, Ju Ho
• Granted Patent: US 11,608,351 B2
• Time in Patent Office: Days
• CPC Class Codes: B01D 2323/40 in-situ membrane formation
• CPC Class Codes: B01D 2325/02831 less than 1 nm
• CPC Class Codes: B01D 67/00793 Dispersing a component, e.g. as particles or powder, in another component
• CPC Class Codes: B01D 69/14111 with nanoscale dispersed material, e.g. nanoparticles
• CPC Class Codes: B01D 69/148 Organic/inorganic mixed matrix membranes
• CPC Class Codes: B01D 71/0281 Zeolites
• CPC Class Codes: C07B 2200/13 Crystalline forms, e.g. polymorphs
• CPC Class Codes: C07F 15/065 without a metal-carbon linkage
• CPC Class Codes: C08K 2201/011 Nanostructured additives
• CPC Class Codes: C08K 5/56 Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond

Abstract

The present invention relates to nanoparticles including a crystal structure-controlled zeolitic imidazolate framework (ZIF) and a method of producing the same. Nanoparticles according to the present invention comprise: metal ions; and an organic ligand coupled to the metal ions, wherein the organic ligand includes an imidazolate-based organic ligand and an alkylamine-based organic ligand.

Claims

1. Nanoparticles including a zeolitic imidazolate framework (ZIF), the nanoparticles comprising:

metal ions; and

an organic ligand coupled to the metal ions, wherein the organic ligand includes an imidazolate-based organic ligand and an alkylamine-based organic ligand.

2. The nanoparticles of claim 1, wherein at least one of a distance between crystal surfaces, a distribution of crystal surfaces and coupling strength in the nanoparticles is adjusted according to use ratio of the alkylamine-based organic ligand.

3. The nanoparticles of claim 2, wherein the alkylamine-based organic ligand is directly combined with the metal ions.

4. The nanoparticles of claim 2, wherein the alkylamine-based organic ligand includes at least any one of primary, secondary and tertiary amines, and includes one or more selected from the group of alkylamines having an alkyl chain of any one length of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, propadecyl, butadecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and nonadecyl.

5. The nanoparticles of claim 2, wherein the organic ligand has a ratio of the imidazolate-based organic ligand to the alkylamine-based organic ligand of 99.9 wt %:

0.1 wt % to 80 wt %;

20 wt %.

6. The nanoparticles of claim 2, wherein the nanoparticles have a distance between (011) crystal surfaces of 11.9 Å

to 12.15 Å

when the metal ions are cobalt, and a distance between (011) crystal surfaces of 12.0 Å

to 12.25 Å

when the metal ions are zinc.

7. The nanoparticles of claim 2, wherein the nanoparticles have a particle size of 100 nm or less.

8. The nanoparticles of claim 7, wherein the nanoparticles have a particle size of 50 nm or less.

9. The nanoparticles of claim 2, wherein the nanoparticles are dispersible in an amphiphilic solvent.

10. The nanoparticles of claim 9, wherein the nanoparticles are dispersible in an amphiphilic solvent to a concentration of about 110 mg/mL.

11. The nanoparticles of claim 2, wherein the nanoparticles have a pore size of 0.1 to 1 nm.

12. The nanoparticles of claim 2, wherein the nanoparticles are dispersed in an amount of 20 to 60 wt % in a polymer matrix to enable a hybrid membrane to be manufactured.

13. The nanoparticles of claim 2, wherein the nanoparticles exhibit a mass reduction of about 3% or less within 400°

C. in TGA test.

14. The nanoparticles of claim 2, wherein an IR peak of Co—

N of the nanoparticles is increased as much as 1 to 3 cm<sup>−

1</sup> by the alkylamine-based organic ligand when the metal ions are cobalt, and an IR peak of Zn—

N of the nanoparticles is increased as much as 1.5 to 4 cm<sup>−

1</sup> by the alkylamine-based organic ligand when the metal ions are zinc.

15. A method of producing nanoparticles including a crystal structure-controlled zeolitic imidazolate framework, the method comprising the steps of:

heating a precursor solution including a metal precursor, an imidazole-based ligand compound and a first polar solvent under stirring;

adding an organic base solution to the precursor solution to obtain a suspension comprising a micro-sized chunk including the zeolitic imidazolate framework;

adding a second polar solvent to the suspension to dilute the suspension; and

obtaining nanoparticles including the zeolitic imidazolate framework from the diluted suspension.

16. The method of claim 15, wherein the metal precursor includes an acetate salt of one or more metals selected from the group consisting of Co, Zn, Sc, Ti, V, Cr, Mn, Fe, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Lr, Rf, Db, Sg, Bh, Hs, Mt, Ds, Rg, and Uub.

17. The method of claim 15, wherein the imidazole-based ligand compound comprises one or more selected from imidazole-based compounds represented by the following chemical formula 1 or chemical formula 2:

18. The method of claim 15, wherein the first and second polar solvents each independently include one or more selected from the group consisting of alcohol, methanol, ethanol, propanol, ethylene glycol, water, dimethylformamide, dimethyl sulfoxide, acetonitrile, and dimethylacetamide.

19. The method of claim 15, wherein the second polar solvent has a pH value of 5 or more.

20. The method of claim 15, wherein the heating process of the precursor solution is isothermally performed.