CN112608492B - Metal organic framework material of cobalt chain based on double-end pyrazole ligand, preparation and benzene adsorption application - Google Patents

Metal organic framework material of cobalt chain based on double-end pyrazole ligand, preparation and benzene adsorption application Download PDF

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CN112608492B
CN112608492B CN202011586928.4A CN202011586928A CN112608492B CN 112608492 B CN112608492 B CN 112608492B CN 202011586928 A CN202011586928 A CN 202011586928A CN 112608492 B CN112608492 B CN 112608492B
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李建荣
何涛
孔祥婧
李铜川
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Abstract

A metal organic framework material of a cobalt chain based on two-end pyrazole ligands, a preparation method and a benzene adsorption application belong to the technical field of crystalline materials. Chemical formula is the chemical formula [ Co (BPZ-X)]，H2BPZ-X is arylbis (1H-pyrazole), X ═ Py, Pz, Pm, pyridinyl, pyrimidinyl, pyrazinyl, respectively. The synthesis of the metal-organic framework is carried out under a closed condition, and an organic ligand aryl di (1H-pyrazole) (H)2BPZ-X) and cobalt nitrate in a mixed solution of N, N-dimethylacetamide and water, and obtaining a crystal of the metal-organic framework material through a solvothermal reaction; the metal organic framework material shows the adsorption performance to aromatic volatile organic compound benzene.

Description

Metal organic framework material of cobalt chain based on double-end pyrazole ligand, preparation and benzene adsorption application
Technical Field
The invention belongs to the technical field of crystalline materials, and relates to a metal-organic coordination polymer material, which is characterized by a cobalt-chain metal-organic framework material, a preparation method thereof and benzene adsorption performance research.
Background
Metal-Organic Frameworks (MOFs) are three-dimensional framework structures formed by connecting inorganic nodes formed by Metal ions/Metal clusters and Organic ligands through coordination bonds. As a class of organic-inorganic porous materials, MOFs have the characteristics of large specific surface area, high porosity, adjustable porosity, various structures and the like, and have wide application prospects in the fields of gas adsorption/separation, sensing, catalysis and the like.
Benzene and derivatives thereof are important components of VOCs in urban outdoor atmosphere and mainly come from automobile exhaust, fuel oil leakage and the like; they are also a major indoor air pollutant, especially in newly erected buildings, which is extremely harmful to humans. Benzene is a primary carcinogen and can cause various diseases such as leukemia and the like. The development of high-efficiency benzene removal technology and related materials has important significance in many aspects. MOFs have great potential in adsorption. The preparation method has important significance in preparing the MOFs material which has strong adsorption effect on trace benzene in the air and good stability.
Disclosure of Invention
The invention aims to provide a metal organic framework material based on cobalt chains of two pyrazole ligands, a preparation method thereof and benzene adsorption performance research.
The invention relates to a metal-organic framework material based on two-end pyrazole ligand, which is characterized in that the chemical molecular formula is [ Co (BPZ-X)]，H2BPZ-X is aryl 1, 4-di (1H-pyrazole), X represents an aromatic ring, X ═ Py, Pz and Pm are respectively pyridyl, pyrimidyl and pyrazinyl.
From the perspective of frame connection construction, the crystal structure of the metal-organic frame belongs to the tetragonal system, and space group is I4122。
In the metal-organic framework, all Co atoms are coordinated in a tetrahedral configuration with four N atoms, the coordinated N being derived from pyrazole groups of four different ligands. The N on both pyrazoles in each ligand in the framework is involved in coordination, and adjacent metal atoms form a zigzag metal chain-like Secondary Building Unit (SBU) through bridged pyrazole groups. The ligands and the metal chain SBU are alternately connected to form a three-dimensional framework structure.
In the metal-organic framework, the bond length of the Co-N bond is within
Figure BDA0002867440130000024
Within the range. Pi-pi stacking occurs between aromatic rings of two adjacent ligands in the framework, and the center distance of the aromatic rings is about
Figure BDA0002867440130000025
A series of novel double-headed pyrazole ligands, characterized in that,the organic ligand is aryl di (1H-pyrazole) (H)2BPZ-X, X stands for aromatic heterocycle, X ═ Py, Pz, Pm, is pyridyl, pyrimidyl, pyrazinyl respectively), the chemical structural formula is:
Figure BDA0002867440130000021
the ligand comprises two pyrazole groups; two pyrazoles in the ligand are in para position to the aromatic ring; the middle aromatic ring is pyridyl, pyrazinyl or pyrimidinyl.
The novel synthesis method of the para-position double-head pyrazole ligand comprises the following two steps:
suzuki coupling: firstly, dibromoaryl and pyrazole boric acid ester protected by tetrahydropyran are added into 1, 4-dioxane and water, potassium carbonate and tetrakis (triphenylphosphine) palladium are added, sealing and vacuumizing are carried out, inert gas is used for protection, and heating reaction is carried out to obtain arylbis (1- (tetrahydro-2H-pyran-2-yl) -1H-pyrazole);
deprotection: heating aryl bis (1- (tetrahydro-2H-pyran-2-yl) -1H-pyrazole) in a hydrochloric acid ethanol solution for deprotection to obtain the aryl bis (1H-pyrazole).
The synthesis method of the metal-organic framework material comprises the following steps:
aryl bis (1H-pyrazole) (H) under sealed conditions2BPZ-X, X ═ Py, Pz, Pm) and cobalt nitrate (Co (NO)3)2·6H2O) in a mixed solution of N, N-Dimethylacetamide (DMA) and deionized water, and obtaining the metal-organic framework crystal through solvothermal reaction.
Further preferred are the organic ligands aryl 1, 4-bis (1H-pyrazole) (H)2The molar ratio of BPZ-X, X ═ Py, Pz and Pm) to cobalt nitrate is 1 (1-4), each 0.05mmol of cobalt nitrate corresponds to 1-4 mL of DMA and 0.4-4 mL of deionized water, the temperature of thermal reaction is 80-130 ℃, and the reaction time is 6-48 hours.
The organic ligand synthesized by the invention belongs to a novel double-end pyrazole ligand. The metal-organic framework has better chemical stability, so that the MOFs has potential application in the adsorption aspect of aromatic volatile organic compounds benzene.
Drawings
FIG. 1 is a structural diagram of two-end pyrazole ligands used for constructing such metal-organic frameworks.
FIG. 2 shows the synthesis of the double pyrazole ligand H of the metal-organic framework2Synthetic route map of BPZ-Py.
FIG. 3 is a diagram of the inorganic building blocks of the metal-organic framework.
Fig. 4 is a schematic three-dimensional structure of the metal-organic framework.
FIG. 5 is a benzene adsorption isotherm diagram of such metal-organic framework materials.
FIG. 6 shows the drawing of Co (BPZ-Py) penetration in such metal-organic framework materials.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Example 1:
weighing ligand H2BPZ-Py (0.06mmol) and Co (NO)3)2·6H2O (0.12mmoL) was placed in a 20mL beaker, 10mL of DMA solution and 6mL of deionized water were added, and the cake was placed in an ultrasonic apparatus and sonicated at room temperature for 5 minutes, after which the solution was transferred to a 20mL Teflon reactor. After sealing, the reaction kettle is placed in an oven at 100 ℃ for reaction for 24 hours. After the reaction is finished, the drying oven is closed, the reaction kettle is opened after the reaction kettle is cooled to room temperature, solid particles obtained in the reaction kettle are filtered and collected, and then DMF and H are sequentially used2O and MeOH (5 mL. times.3) and observed under a microscope to give a purplish red block crystal [ Co (BPZ-Py)](yield: 59% based on H)2BPZ-Py ligand).
Example 2:
weighing ligand H2BPZ-Py (0.06mmol) and Co (NO)3)2·6H2O (0.12mmoL) was placed in a 20mL beaker, 12mL of DMA solution and 4mL of deionized water were added, and the cake was placed in an ultrasonic apparatus and sonicated at room temperature for 5 minutes, after which the solution was transferred to a 20mL Teflon reactor. After being sealed, the reaction kettle is arranged inThe reaction was carried out in an oven at 120 ℃ for 24 hours. After the reaction is finished, the drying oven is closed, the reaction kettle is opened after the reaction kettle is cooled to room temperature, solid particles obtained in the reaction kettle are filtered and collected, and then DMF and H are sequentially used2Washed with MeOH (5 mL. times.3), and observed under a microscope to obtain magenta block crystals [ Co (BPZ-Py)](yield: 51% based on H)2BPZ-Py ligand).
Example 3
Weighing ligand H2BPZ-Pz (0.06mmol) and Co (NO)3)2·6H2O (0.14mmoL) was placed in a 20mL beaker, 10mL of DMA solution and 4mL of deionized water were added, and the cake was placed in an ultrasonic apparatus and sonicated at room temperature for 5 minutes, after which the solution was transferred to a 20mL Teflon reactor. After sealing, the reaction kettle is placed in an oven at 120 ℃ for reaction for 36 hours. After the reaction is finished, the drying oven is closed, the reaction kettle is opened after the reaction kettle is cooled to room temperature, solid particles obtained in the reaction kettle are filtered and collected, and then DMF and H are sequentially used2O and MeOH (5 mL. times.3) and observed under a microscope to give a purplish red block crystal [ Co (BPZ-Pz) ]](yield: 63% based on H)2BPZ-Pz ligand).
Example 4
Weighing ligand H2BPZ-Pm (0.06mmol) and Co (NO)3)2·6H2O (0.18mmoL) was placed in a 20mL beaker, 10mL of DMA solution and 7mL of deionized water were added, and the cake was placed in an ultrasonic apparatus and sonicated at room temperature for 5 minutes, after which the solution was transferred to a 20mL Teflon reactor. After sealing, the reaction kettle is placed in an oven at 130 ℃ for reaction for 24 hours. After the reaction is finished, the drying oven is closed, the reaction kettle is opened after the reaction kettle is cooled to room temperature, solid particles obtained in the reaction kettle are filtered and collected, and then DMF and H are sequentially used2O and MeOH (5 mL. times.3) and observed under a microscope to give a purplish red block crystal [ Co (BPZ-Pm)](yield: 58% based on H)2BPZ-Pm ligand).
The test results of the products obtained in the above examples are the same, and are specifically as follows:
(1) determination of crystal structure:
selecting single crystal sample with proper size, and utilizing at room temperatureThe data were collected on a Rigaku Supernova single crystal instrument. Data collection Using Cu-Ka monochromated by graphite monochromator
Figure BDA0002867440130000052
A target ray. Data absorption correction was done using SCALE3 absack software. The crystal structure was resolved by direct methods using the program SHELXTL-97. Firstly, determining all non-hydrogen atom coordinates by using a difference function method and a least square method, obtaining the hydrogen atom position by using a theoretical hydrogenation method, and then refining the crystal structure by using SHELXTL-97. The structure is shown in fig. 3 to 4. The crystallographic data are shown in table 1.
TABLE 1 crystallography data for metal organic framework materials
Figure BDA0002867440130000051
Figure BDA0002867440130000061
FIG. 1 is a structural diagram of two-end pyrazole ligands for constructing such metal-organic frameworks
FIG. 2 shows the double pyrazole ligand H of the metal-organic framework2The synthetic route map for BPZ-Py shows: firstly, adding 2, 5-dibromopyridine and tetrahydropyrane protected pyrazole boric acid ester into 1, 4-dioxane and water, adding potassium carbonate and tetrakis (triphenylphosphine) palladium, sealing, vacuumizing, protecting by inert gas, and heating to react to obtain 2, 5-bis (1- (tetrahydro-2H-pyran-2-yl) -1H-pyrazole-4-yl) pyridine; then heating 2, 5-bis (1- (tetrahydro-2H-pyran-2-yl) -1H-pyrazole-4-yl) pyridine in a hydrochloric acid ethanol solution to remove protection to obtain the 2, 5-bis (1H-pyrazole-4-yl) pyridine.
The structure diagram of the chain inorganic building block of FIG. 3 shows: the inorganic nodes contained in the framework are chain-shaped Co-based SBUs.
The block diagram of fig. 4 shows: a three-dimensional stacking diagram of the metal-organic framework.
(2) Adsorption of aromatic volatile organic compound benzene
FIG. 5 is the adsorption isotherm of the material of the present invention on benzene, which shows that the material can effectively adsorb benzene. FIG. 5 is a benzene adsorption isotherm of the inventive material in a thermostated water bath at 298K, as tested by a gas adsorber.
FIG. 6 shows the Co (BPZ-Py) desorption diagram of the material of the present invention, which shows that the material can effectively adsorb benzene with low concentration of volatile aromatic compound for a long time. FIG. 6 is a graph of breakthrough adsorption where saturation of adsorption can be achieved in 50 hours, simulating the passage of air containing a low concentration of benzene (10ppm) through the material.

Claims (4)

1. A cobalt-chain metal-organic framework material based on two-end pyrazole ligands is characterized in that the chemical formula is [ Co (BPZ-X)]，H2BPZ-X is aryl 1, 4-di (1H-pyrazole), X represents an aromatic ring, X ═ Py, Pz and Pm are respectively pyridyl, pyrimidyl and pyrazinyl; said H2The chemical structure of BPZ-X is as follows:
Figure FDA0003587779610000011
from the viewpoint of framework connection construction, the crystal structure of the metal-organic framework belongs to a tetragonal system, and the space group is I4122；
In the metal-organic framework, all Co atoms are coordinated in a tetrahedral configuration with four N atoms, the coordinated N being derived from pyrazole groups of four different ligands; n on two pyrazoles in each ligand in the framework participates in coordination, adjacent metal atoms form a zigzag metal chain-shaped secondary building unit SBU through bridged pyrazole groups, and the ligands and the metal chain-shaped SBU are alternately connected to form a three-dimensional framework structure.
2. A metal-organic framework material based on cobalt chains of two-headed pyrazole ligands according to claim 1, characterized in that the bond length of the Co-N bond in the metal-organic framework is within
Figure FDA0003587779610000012
Within the range; the aromatic rings of two adjacent ligands in the framework are subjected to pi-pi stacking, and the distance between the centers of the aromatic rings is
Figure FDA0003587779610000013
3. The process for the preparation of a metal-organic framework material based on cobalt chains of a bipodal pyrazole ligand according to claim 1, characterized in that the aryl 1, 4-bis (1H-pyrazole) (H) is prepared under sealed conditions2BPZ-X, X ═ Py, Pz and Pm) and cobalt nitrate are subjected to solvothermal reaction in a mixed solution of N, N-Dimethylacetamide (DMA) and deionized water to obtain a crystal of the metal-organic framework; organic ligand aryl 1, 4-bis (1H-pyrazole) (H)2The molar ratio of BPZ-X, X is Py, Pz and Pm) to cobalt nitrate is 1 (1-4), each 0.05mmol of cobalt nitrate corresponds to 1-4 mL of DMA and 0.4-4 mL of deionized water, the temperature of the thermal reaction is 80-130 ℃, and the reaction time is 6-48 hours.
4. Use of a metal-organic framework material based on cobalt chains of double-headed pyrazole ligands according to claim 1 as adsorbent for aromatic volatile organic compounds.
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