Bimetallic coordination metal-organic framework material, preparing method thereof, and application thereof

Patent metadata

Field	Value
Publication number	US-11945774-B2
Application number	US-202318109843-A
Country	US
Kind code	B2
Filing date	Feb 14, 2023
Priority date	Feb 15, 2022
Publication date	Apr 2, 2024
Grant date	Apr 2, 2024

Abstract

The present disclosure provides a bimetallic coordination metal-organic framework material, a preparing method thereof, and an application thereof. In the bimetallic coordination metal-organic framework material, carboxyl groups and soft groups of ligands are coordinated with coordination metal ions to assemble a structure having space and functions divided into covalent charge carrier layers and charge storage ion layers. Further, through the conjugation effect, the bimetallic coordination metal-organic framework material has unique electromagnetic properties, good electrical conductivity, and magnetic coupling performance. Thus, the bimetallic coordination metal-organic framework material is used as superconducting materials, conductive materials, semiconductor materials, or electromagnetic materials. Through the preparing method, the structure including the covalent charge carrier layers and the charge storage ion layers is assembled, so the bimetallic coordination metal-organic framework material has unique electromagnetic properties.

First claim

What is claimed is:

1. A bimetallic coordination metal-organic framework material, comprising:
an M1 two-dimensional coordination network structure comprising M1 coordination layers; and
M2 coordination structures embedded between the M1 coordination layers;
wherein coordination metal ions M1 are coordinated with ligands to form the M1 two-dimensional coordination network structure; each of the M2 coordination structures is a zero-dimensional M2 coordination structure, a one-dimensional M2 coordination structure, or a two-dimensional M2 coordination structure; coordination metal ions M2 are coordinated with the ligands to form the M2 coordination structures;
wherein each of the ligands is a compound containing a carboxyl group and soft groups; the coordination metal ions M1 form a M1 two-dimensional coordination network structure with the soft groups or form the M1 two-dimensional coordination network structure with the soft groups and carboxyl groups of the ligands; the coordination metal ions M2 and oxygen atoms of the carboxyl groups of the ligands form the M2 coordination structures embedded between the M1 coordination layers;
wherein the soft groups are —XH, and X is selected from S and Se.

2. The bimetallic coordination metal-organic framework material according to claim 1 , wherein the M2 coordination structures comprise one or more of H2O, hydroxide, and halogen.

3. The bimetallic coordination metal-organic framework material according to claim 1 , wherein the coordination metal ions M1 are same as or different from the coordination metal ions M2; the coordination metal ions M1 and the coordination metal ions M2 are selected from one or more of transition metal ions, Ga, In, Sn, Tl, Pb, and Bi.

4. The bimetallic coordination metal-organic framework material according to claim 1 , wherein the ligands are an aromatic compound, the carboxyl group and the soft groups of each of the ligand are directly or indirectly connected to an aromatic ring.

5. The bimetallic coordination metal-organic framework material according to claim 4 , wherein each of the ligands comprises at least one carboxyl group and at least two soft groups.

6. A preparing method for the bimetallic coordination metal-organic framework material according to claim 1 , comprising following steps:
S 11 : weighing the ligands and metal salt, and adding the ligands and the metal salt into a container;
S 12 : adding a mixed solution containing water and an organic solvent into the container, and sealing the container; and
S 13 : placing the container in an oven and heating to obtain the bimetallic coordination metal-organic framework material.

7. The preparing method for the bimetallic coordination metal-organic framework material according to claim 6 , wherein replacing the metal salt in the step S 11 with a metal oxide; wherein the preparing method further comprises steps of preparing a metal oxide suspension:
S 21 : dissolving the metal salt in the water to obtain a solution A, and dissolving NaBH 4 in the water to obtain a solution B; then adding the solution B into the solution A for reaction; and centrifuging, washing, and vacuum drying a product after reaction to obtain a metal oxide nanosheet; and
S 22 : dispersing the metal oxide nanosheet prepared in the step S 21 in the water to obtain the metal oxide suspension;
wherein the container is a reaction kettle; when preparing the bimetallic coordination metal-organic framework material, the ligands are weighed and added into the reaction kettle together with the mixed solution containing the water and the organic solvent; the metal oxide suspension prepared in the step S 22 is added into the reaction kettle, and a solvothermal reaction is performed to obtain the bimetallic coordination metal-organic framework material.

8. The preparing method for the bimetallic coordination metal-organic framework material according to claim 6 , wherein in the mixed solution containing the water and the organic solvent, the organic solvent is selected from one or more of N,N-Dimethylformamide (DMF), N,N-diethylformamide (DEF), and ethanol (EtOH); wherein a volume ratio of the organic solvent to the water is 1: 2-8;
wherein when the mixed solution is added, a regulator is simultaneously added; and the regulator is selected from one or more of formic acid, acetic acid, and trifluoroacetic acid;
wherein a molar ratio of the ligands to metal ions of the metal salt is 1: 2.5-4.

9. An application of the bimetallic coordination metal-organic framework material according to claim 1 , wherein the bimetallic coordination metal-organic framework material is applied in superconducting materials, conductive materials, semiconductor materials, or electromagnetic materials.

Assignees

• Univ Guangdong Technology
• Univ City Hong Kong

Inventors

• He Jun
• Hu Jieying
• Tang Liangming
• Liu Zhiqing
• Ye Xinhe
• Zhang Gengyuan
• Xu Zhengtao

Classifications

• C07C51/418 Primary

  Preparation of metal complexes containing carboxylic acid moieties · CPC title

• C08G83/008 Primary

  Supramolecular polymers · CPC title

• C07C323/62 Primary

  having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton · CPC title

• C07F19/005

  without metal-C linkages · CPC title

• C07F15/065

  without a metal-carbon linkage · CPC title