A kind of supertetrahedral metal-organic framework material, its preparation method and application

Abstract

The invention discloses a hypertetrahedral metal-organic framework constructed based on a window-space oriented assembly strategy and its preparation method and application; a novel window-space oriented assembly strategy is proposed, and a series of supertetrahedral building unit structures based on angles are designed and synthesized. Metal organic framework materials ST‑sod‑MOFs with ultramicroporous quadrilateral windows and mesoporous sodalite cages are built in a shared way. The general structure formula of this type of metal organic framework materials is: [M 3 (OH / O)(H 2 O / F)(btc) 2 (tpt) 2 / 3 ], where M is a metal ion or a combination of two different metal ions, such as magnesium, manganese, iron, cobalt, nickel, zinc, aluminum, scandium, gallium, indium and other single metal ions or titanium, vanadium, scandium, A binary combination of gallium, indium, and one of iron, cobalt, nickel, and magnesium, respectively. This type of metal organic framework material is a three-dimensional sodalite network skeleton formed by trinuclear metal ion cluster nodes and organic ligands through coordination bonds. Among them, ST‑sod‑Co / Ti not only has good thermal stability and high acid and alkali resistance stability, but also 2 h 2 / CO 2 Good performance in separation.

Description

technical field

[0001] The invention belongs to the technical field of porous crystalline material preparation and gas adsorption and separation, and specifically relates to a supertetrahedral metal organic framework material, its preparation method and application. Background technique

[0002] Metal-organic frameworks (MOFs) materials, also known as porous coordination polymers (Porous coordination polymers, PCPs), usually refer to the formation of metal ions or metal clusters and organic ligands through a self-assembly process with infinite periodicity. Crystalline materials with a network structure have both the characteristics of organic polymers and inorganic compounds. It has attracted ongoing attention due to its potential applications in gas storage and separation, heterogeneous catalysis, and drug delivery.

[0003] The performance of MOFs is highly dependent on the resulting network topology, which is greatly influenced by the coordination geometry of metal nodes...

Examples

Embodiment 1

[0047] The preparation method of ST-sod-Co in ST-sod-MOFs comprises the following steps:

[0048] CoSO 4 ·7H 2 O (0.0633g, 0.225mmol), 2,4,6-tris(4-pyridyl)-1,3,5-triazine (0.0162g, 0.052mmol) and 1,3,5-benzenetricarboxylate (0.0324g, 0.154mmol) into a 20ml glass bottle; then drop into N,N-dimethylformamide (4mL) / methanol (1mL) solution; then add 200uL of HBF 4 (tetrafluoroboric acid, 50 wt% aqueous solution), sonicated for 30 min; finally, the mixture was sealed and heated to 110° C. for 10 days. After collection, DMF washing and vacuum drying, the target product red cubic crystal ST-sod-Co was obtained.

[0049] Refer to attached Figure 4 , ST-sod-Co at 77K for N 2 The results of adsorption measurements indicated that ST-sod-Co exhibited a reversible type I adsorption behavior with a stepwise N 2 Adsorption isotherm, which indicates the presence of mesoporous cages in the framework. The saturated adsorption capacity reaches 400cm 3 g -1 , BET surface area is 1310m ...

Embodiment 2

[0053] The preparation method of ST-sod-Ni in ST-sod-MOFs comprises the following steps:

[0054] First Ni(NO 3 ) 2 ·6H 2 O (0.1308g, 0.45mmol), 2,4,6-tris(4-pyridyl)-1,3,5-triazine (0.0310g, 0.10mmol) and 1,3,5-benzenetricarboxylate (0.0632g, 0.30mmol) into a 20ml glass bottle; then drop N,N-dimethylformamide (3mL) / N,N-dimethylacetamide (3mL) / methanol (1mL) solution; Then add 400uL of HSiF 6 (fluorosilicic acid, 25 wt% aqueous solution), sonicated for 30 min; finally, the mixture was sealed and heated to 125° C. for 7 days. After collection, DMA washing and vacuum drying, the target product green cubic crystal ST-sod-Ni was obtained.

[0055] Refer to attached Figure 4 , ST-sod-Ni at 77K for N 2 The results of adsorption measurements indicated that ST-sod-Ni exhibited a reversible type I adsorption behavior with a stepwise N 2 Adsorption isotherm, which indicates the presence of mesoporous cages in the framework. The saturated adsorption capacity reaches 400cm 3 g ...

Embodiment 3

[0059] The preparation method of ST-sod-Co / Ti in ST-sod-MOFs comprises the following steps:

[0060] CoCl 2 ·6H 2 O (0.0734g, 0.31mmol), titanium dichloride (0.0375g, 0.15mmol), 2,4,6-tris(4-pyridyl)-1,3,5-triazine (0.0310g, 0.10mmol) and 1,3,5-benzenetricarboxylate (0.0632g, 0.30mmol) into a 20ml glass bottle; then drop into N,N-dimethylformamide (3mL) / N,N-dimethyl Acetamide (3mL) / methanol (1mL) solution; then add 400uL of HSiF 6 (fluorosilicic acid, 35 wt% aqueous solution), sonicated for 30 min; finally, the mixture was sealed and heated to 140° C. for 3 days. After collection, DMA washing and vacuum drying, the target product red polyhedral crystal ST-sod-Co / Ti was obtained.

[0061] Refer to attached Figure 4 , ST-sod-Co / Ti at 77K for N 2 The results of adsorption measurements indicated that ST-sod-Co / Ti exhibited a reversible type I adsorption behavior with a stepwise N 2 Adsorption isotherm, which indicates the presence of mesoporous cages in the framework. The...

technical field

[0001] The invention belongs to the technical field of porous crystalline material preparation and gas adsorption and separation, and specifically relates to a supertetrahedral metal organic framework material, its preparation method and application. Background technique

[0002] Metal-organic frameworks (MOFs) materials, also known as porous coordination polymers (Porous coordination polymers, PCPs), usually refer to the formation of metal ions or metal clusters and organic ligands through a self-assembly process with infinite periodicity. Crystalline materials with a network structure have both the characteristics of organic polymers and inorganic compounds. It has attracted ongoing attention due to its potential applications in gas storage and separation, heterogeneous catalysis, and drug delivery.

[0003] The performance of MOFs is highly dependent on the resulting network topology, which is greatly influenced by the coordination geometry of metal nodes...

Examples

Embodiment 1

[0047] The preparation method of ST-sod-Co in ST-sod-MOFs comprises the following steps:

[0048] CoSO 4 ·7H 2 O (0.0633g, 0.225mmol), 2,4,6-tris(4-pyridyl)-1,3,5-triazine (0.0162g, 0.052mmol) and 1,3,5-benzenetricarboxylate (0.0324g, 0.154mmol) into a 20ml glass bottle; then drop into N,N-dimethylformamide (4mL) / methanol (1mL) solution; then add 200uL of HBF 4 (tetrafluoroboric acid, 50 wt% aqueous solution), sonicated for 30 min; finally, the mixture was sealed and heated to 110° C. for 10 days. After collection, DMF washing and vacuum drying, the target product red cubic crystal ST-sod-Co was obtained.

[0049] Refer to attached Figure 4 , ST-sod-Co at 77K for N 2 The results of adsorption measurements indicated that ST-sod-Co exhibited a reversible type I adsorption behavior with a stepwise N 2 Adsorption isotherm, which indicates the presence of mesoporous cages in the framework. The saturated adsorption capacity reaches 400cm 3 g -1 , BET surface area is 1310m ...

Embodiment 2

[0053] The preparation method of ST-sod-Ni in ST-sod-MOFs comprises the following steps:

[0054] First Ni(NO 3 ) 2 ·6H 2 O (0.1308g, 0.45mmol), 2,4,6-tris(4-pyridyl)-1,3,5-triazine (0.0310g, 0.10mmol) and 1,3,5-benzenetricarboxylate (0.0632g, 0.30mmol) into a 20ml glass bottle; then drop N,N-dimethylformamide (3mL) / N,N-dimethylacetamide (3mL) / methanol (1mL) solution; Then add 400uL of HSiF 6 (fluorosilicic acid, 25 wt% aqueous solution), sonicated for 30 min; finally, the mixture was sealed and heated to 125° C. for 7 days. After collection, DMA washing and vacuum drying, the target product green cubic crystal ST-sod-Ni was obtained.

[0055] Refer to attached Figure 4 , ST-sod-Ni at 77K for N 2 The results of adsorption measurements indicated that ST-sod-Ni exhibited a reversible type I adsorption behavior with a stepwise N 2 Adsorption isotherm, which indicates the presence of mesoporous cages in the framework. The saturated adsorption capacity reaches 400cm 3 g ...

Embodiment 3

[0059] The preparation method of ST-sod-Co / Ti in ST-sod-MOFs comprises the following steps:

[0060] CoCl 2 ·6H 2 O (0.0734g, 0.31mmol), titanium dichloride (0.0375g, 0.15mmol), 2,4,6-tris(4-pyridyl)-1,3,5-triazine (0.0310g, 0.10mmol) and 1,3,5-benzenetricarboxylate (0.0632g, 0.30mmol) into a 20ml glass bottle; then drop into N,N-dimethylformamide (3mL) / N,N-dimethyl Acetamide (3mL) / methanol (1mL) solution; then add 400uL of HSiF 6 (fluorosilicic acid, 35 wt% aqueous solution), sonicated for 30 min; finally, the mixture was sealed and heated to 140° C. for 3 days. After collection, DMA washing and vacuum drying, the target product red polyhedral crystal ST-sod-Co / Ti was obtained.

[0061] Refer to attached Figure 4 , ST-sod-Co / Ti at 77K for N 2 The results of adsorption measurements indicated that ST-sod-Co / Ti exhibited a reversible type I adsorption behavior with a stepwise N 2 Adsorption isotherm, which indicates the presence of mesoporous cages in the framework. The...

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