Multicore and multivariable metal-organic framework materials and their synthesis and application

Abstract

The invention provides a multi-core multi-variable metal organic framework material and its synthesis and application. The metal organic framework material, its molecular formula is {(NH 2 (CH 3 ) 2 )[W 9 (μ 3 -OH) 2 (μ 4 -OH)(X) 2 (Y) 8 (Z)]} n ; Among them, W is Co 2+ or Ni 2+ ; X is 4,4',4"'-(pyridine-2,4,6-triyl)tribenzoic acid, phenyl-1,3,5-tribenzoic acid, 4,4',4"-all Triazine‑2,4,6‑triylbenzoic acid; Y is isonicotinic acid, trifluoroisonicotinic acid, trimethylisonicotinic acid; Z is terephthalic acid, naphthalene dicarboxylic acid, thiophenedicarboxylic acid, Dibromobenzoic acid; n is the number of repeating units. The metal organic framework material can selectively adsorb acetylene in carbon dioxide. And it can be used repeatedly, the adsorption cost is low, and it has a great application prospect in the industrial purification of acetylene and the recovery of acetylene.

Description

technical field

[0001] The invention belongs to the technical field of metal-organic framework materials, and in particular relates to a multi-core and multi-variable metal-organic framework material and its synthesis and application. Background technique

[0002] Acetylene (C 2 h 2 ) is a highly flammable and reactive gas widely used in lighting, welding and cutting metals, and also as a basic raw material for the manufacture of acetaldehyde, acetic acid, benzene, synthetic rubber and synthetic fibers. Usually high-purity C 2 h 2 is the most basic requirement to safeguard these applications; however, impurities such as carbon dioxide (CO 2 ) are always present in acetylene production. C 2 h 2 and CO 2 Their similar molecular size, sublimation temperature, and critical temperature make their separation challenging.

[0003] At present, only a few refineries use cryogenic distillation to convert C 2 h 2 with CO 2 Separation, but the energy consumption of the separ...

Examples

Embodiment 1

[0042] In this embodiment, a method for preparing a multi-nuclear and multi-variable metal-organic framework Co-PTB-BDC-ina is involved, including the following steps:

[0043] (1) Under sealed conditions, the H 3 PTB (0.05 mmol), CoCl 2 ·6H 2 O (0.1 mmol), Hina (0.1 mmol) and H 2 BDC (0.05 mmol) was added to 2 mL of N,N-dimethylacetamide ( ) and mix well, add 6 drops of fluoboric acid.

[0044] (2) Heating and reacting at 120°C for 2 days to obtain pink blocky crystals, which are multi-nuclear and multi-variable metal-organic framework materials.

[0045] The structure of the crystal was determined by Agilent Technologies SuperNova single crystal diffractometer test, the test results showed that: its molecular formula is {(NH 2 (CH 3 ) 2 )[Co 9 (µ 3 -OH) 2 (µ 4 -OH)(PTB) 2 (ina) 8 (BDC)]} n , where H 3 PTB is 4, 4’,4’’’-(pyridine-2,4,6-triyl)tribenzoic acid, the structural formula is , Hina is isonicotinic acid, H 2 BDC is terephthalic acid.

[0046] The ...

Embodiment 2

[0049] This embodiment relates to the preparation method of Co-PTB-NDC-ina multi-core multi-variable metal-organic framework, including the following steps:

[0050] Experimental procedure is consistent with embodiment 1, except ligand terephthalic acid (H 2 BDC) was replaced by naphthalene dicarboxylic acid (H 2 NDC), pink crystals were obtained.

[0051] Its structure is similar to that of Example 1, except that the ligand is changed from H 2 Change BDC to H 2 NDC.

Embodiment 3

[0053] This embodiment relates to the preparation method of Co-PTB-BDC-Fina multi-core multi-variable metal-organic framework, including the following steps:

[0054] The experimental procedure was the same as in Example 1, except that the ligand was changed from isonicotinic acid (Hina) to trifluoroisonicotinic acid (FHina), and pink crystals were obtained.

[0055] Its structure was tested by single crystal diffraction to be similar to the crystal structure of Example 1, except that the ligand was changed from Hina to FHina.

technical field

[0001] The invention belongs to the technical field of metal-organic framework materials, and in particular relates to a multi-core and multi-variable metal-organic framework material and its synthesis and application. Background technique

[0002] Acetylene (C 2 h 2 ) is a highly flammable and reactive gas widely used in lighting, welding and cutting metals, and also as a basic raw material for the manufacture of acetaldehyde, acetic acid, benzene, synthetic rubber and synthetic fibers. Usually high-purity C 2 h 2 is the most basic requirement to safeguard these applications; however, impurities such as carbon dioxide (CO 2 ) are always present in acetylene production. C 2 h 2 and CO 2 Their similar molecular size, sublimation temperature, and critical temperature make their separation challenging.

[0003] At present, only a few refineries use cryogenic distillation to convert C 2 h 2 with CO 2 Separation, but the energy consumption of the separ...

Examples

Embodiment 1

[0042] In this embodiment, a method for preparing a multi-nuclear and multi-variable metal-organic framework Co-PTB-BDC-ina is involved, including the following steps:

[0043] (1) Under sealed conditions, the H 3 PTB (0.05 mmol), CoCl 2 ·6H 2 O (0.1 mmol), Hina (0.1 mmol) and H 2 BDC (0.05 mmol) was added to 2 mL of N,N-dimethylacetamide ( ) and mix well, add 6 drops of fluoboric acid.

[0044] (2) Heating and reacting at 120°C for 2 days to obtain pink blocky crystals, which are multi-nuclear and multi-variable metal-organic framework materials.

[0045] The structure of the crystal was determined by Agilent Technologies SuperNova single crystal diffractometer test, the test results showed that: its molecular formula is {(NH 2 (CH 3 ) 2 )[Co 9 (µ 3 -OH) 2 (µ 4 -OH)(PTB) 2 (ina) 8 (BDC)]} n , where H 3 PTB is 4, 4’,4’’’-(pyridine-2,4,6-triyl)tribenzoic acid, the structural formula is , Hina is isonicotinic acid, H 2 BDC is terephthalic acid.

[0046] The ...

Embodiment 2

[0049] This embodiment relates to the preparation method of Co-PTB-NDC-ina multi-core multi-variable metal-organic framework, including the following steps:

[0050] Experimental procedure is consistent with embodiment 1, except ligand terephthalic acid (H 2 BDC) was replaced by naphthalene dicarboxylic acid (H 2 NDC), pink crystals were obtained.

[0051] Its structure is similar to that of Example 1, except that the ligand is changed from H 2 Change BDC to H 2 NDC.

Embodiment 3

[0053] This embodiment relates to the preparation method of Co-PTB-BDC-Fina multi-core multi-variable metal-organic framework, including the following steps:

[0054] The experimental procedure was the same as in Example 1, except that the ligand was changed from isonicotinic acid (Hina) to trifluoroisonicotinic acid (FHina), and pink crystals were obtained.

[0055] Its structure was tested by single crystal diffraction to be similar to the crystal structure of Example 1, except that the ligand was changed from Hina to FHina.

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