Ordered macroporous metal-organic framework single crystals and preparation method thereof

Patent metadata

Field	Value
Publication number	US-11241679-B2
Application number	US-201716330103-A
Country	US
Kind code	B2
Filing date	Nov 27, 2017
Priority date	Sep 13, 2017
Publication date	Feb 8, 2022
Grant date	Feb 8, 2022

Abstract

An ordered macroporous metal-organic framework single crystals and a preparation method therefor. In the method, a three-dimensional structure constructed by polymer microspheres is used as a template; 2-methylimidazole and zinc nitrate, precursors of MOFs, are firstly deposited in the three-dimensional template; the three-dimensional template containing the precursors is soaked in a mixed solution of ammonia water and methanol subsequently, and the three-dimensional template is taken out after crystallization; the three-dimensional template is soaked in an organic solvent to remove the macromolecular three-dimensional template, and the ordered macroporous MOF single crystals is obtained through centrifugal separation. The ordered macroporous MOF single crystals have a basic framework of zeolitic imidazolate framework-8, and structurally include highly-ordered macro-pores whose pore size may be controlled to be between 50 and 2000 nm based on a size of the used template.

First claim

What is claimed is:

1. A preparation method of ordered macroporous metal-organic framework single crystals, comprising the following steps:
(1) dispersing polymer microspheres into a solvent, and preparing, through filtering or centrifugation, a three-dimensional template having periodic pore channels that is constructed by the polymer microspheres;
(2) adding the three-dimensional template obtained in step (1) into a solution of 2-methylimidazole and zinc nitrate, standing still for 0 to 12 hours followed by vacuum treating for 0 to 2 hours, and then taking out the three-dimensional template and drying to obtain a microspherical three-dimensional template containing the 2-methylimidazole and the zinc nitrate;
(3) adding the microspherical three-dimensional template containing the 2-methylimidazole and the zinc nitrate obtained in step (2) into a mixed solution of ammonia water and methanol, vacuum treating for 0 to 2 hours followed by standing still for 1 to 48 hours, and then filtering, washing and drying;
(4) adding a solid obtained after drying in step (3) into an organic solvent for soaking, and then washing the solid and obtaining the macroporous metal-organic framework single crystals through centrifugal separation.

2. The preparation method according to claim 1 , wherein the polymer microspheres in step (1) are uniformly sized polystyrene microspheres, polymethylmethacrylate microspheres, chitosan microspheres or polylactic acid microspheres.

3. The preparation method according to claim 1 , wherein the solvent in step (1) is one or a mixture of methanol, ethanol, acetone, deionized water, dichloromethane and ethyl acetate.

4. The preparation method according to claim 1 , wherein a molar ratio of the 2-methylimidazole to the zinc nitrate in step (2) is (0.5-5):1.

5. The preparation method according to claim 1 , wherein a solvent of the solution in step (2) is one or a mixture of methanol, ethanol, acetone, deionized water, dichloromethane and ethyl acetate.

6. The preparation method according to claim 1 , wherein a mass ratio of the 2-methylimidazole to the solvent in the solution in step (2) is 0.001 to 0.5 g/ml.

7. The preparation method according to claim 1 , wherein a volume ratio of the methanol to the ammonia water in step (3) is (0-10):1.

8. The preparation method according to claim 1 , wherein the organic solvent in step (4) is one or a mixture of N,N-dimethylformamide, toluene, tetrahydrofuran, dichloromethane and chloroform.

9. The preparation method according to claim 1 , wherein the soaking in step (4) lasts for 1 to 48 hours.

10. An ordered macroporous metal-organic framework single crystals prepared by using the preparation method according to claim 1 .

11. An ordered macroporous metal-organic framework single crystals prepared by using the preparation method according to claim 2 .

12. An ordered macroporous metal-organic framework single crystals prepared by using the preparation method according to claim 3 .

13. An ordered macroporous metal-organic framework single crystals prepared by using the preparation method according to claim 4 .

14. An ordered macroporous metal-organic framework single crystals prepared by using the preparation method according to claim 5 .

15. An ordered macroporous metal-organic framework single crystals prepared by using the preparation method according to claim 6 .

16. An ordered macroporous metal-organic framework single crystals prepared by using the preparation method according to claim 7 .

17. An ordered macroporous metal-organic framework single crystals prepared by using the preparation method according to claim 8 .

18. An ordered macroporous metal-organic framework single crystals prepared by using the preparation method according to claim 9 .

Assignees

• Univ South China Tech

Inventors

• Shen Kui
• Li Yingwei
• Cao Yonghai
• Chen Junying

Classifications

• B01J37/0203

  the impregnation liquid containing organic compounds · CPC title

• B01J31/1691 Primary

  Coordination polymers, e.g. metal-organic frameworks [MOF] (preparation of metal complexes containing carboxylic acid moieties C07C51/418; MOF's per se C07F) · CPC title

• C08G83/00

  Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00 · CPC title

• B01J37/06

  Washing {(B01J37/0009, B01J37/0018 take precedence)} · CPC title

• C07F3/06

  Zinc compounds · CPC title