CN112295546A - Zinc complex with porous structure and preparation method thereof - Google Patents

Zinc complex with porous structure and preparation method thereof Download PDF

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CN112295546A
CN112295546A CN202011357190.4A CN202011357190A CN112295546A CN 112295546 A CN112295546 A CN 112295546A CN 202011357190 A CN202011357190 A CN 202011357190A CN 112295546 A CN112295546 A CN 112295546A
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zinc
zinc complex
porous structure
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terpyridine
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CN112295546B (en
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李星
刘啸影
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Ningbo University
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Abstract

The invention discloses a zinc complex with a porous structure and a preparation method thereof, and is characterized in that the complex is an organic-inorganic hybrid coordination compound containing zinc, 3 ', 5,5 ' -biphenyltetracarboxylic acid and 2,2', 6', 2' -terpyridine ligand, and the molecular formula of the complex is C23H14N3O4Zn, crystal system is orthogonal, space group is Fddd, cell parameter
Figure DDA0002802896630000011
Figure DDA0002802896630000012
α ═ β ═ γ ═ 90 °; the complex has a porous structure and can be used in the fields of gas adsorption, ion exchange and the like. The invention has simple synthesis steps and low costLow cost and suitability for batch production.

Description

Zinc complex with porous structure and preparation method thereof
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a zinc complex with a porous structure and a preparation method thereof.
Background
A Metal-Organic Framework (MOFs) material is a composite porous material formed by connecting inorganic Metal ions and Organic ligands, and has attracted much attention of scientists due to its special structure. MOFs materials have particular advantages over inorganic or organic porous materials: the pore structure is highly ordered; the size of the hole can be regulated and controlled; the functional groups on the surface of the material can be regulated and controlled through chemical design, and the unique properties enable the material to have good application prospects in multiple fields, particularly the application of the material in aspects of gas adsorption, separation and purification, catalysis, microreactor, negative ion exchange and the like, and the material becomes one of the most active research fields in chemical and material subjects in recent years. The 3,3 ', 5 ', 5 ' -biphenyltetracarboxylic acid has a large conjugated plane structure, four carboxyl groups can be connected with metal ions in different directions, and two benzene rings can generate certain torsion, so that a rich and diverse porous metal organic coordination compound can be finally formed, and the porous metal organic coordination compound has wide application in the aspects of ion exchange, gas storage separation, nonlinear optics and the like.
Disclosure of Invention
The invention aims to solve the technical problem of providing a zinc complex with a porous structure and a preparation method thereof, and the preparation method has the advantages of simple process, good repeatability, high yield, mild synthesis conditions and low cost.
The technical scheme adopted by the invention for solving the technical problems is as follows: a zinc complex with porous structure is an organic-inorganic hybrid coordination compound containing zinc, 3 ', 5,5 ' -biphenyltetracarboxylic acid and 2,2', 6', 2' -terpyridine ligand, and the structure formula of the complex is [ Zn (tpy) ((L))0.5](tpy stands for 2,2':6', 2' -terpyridine, L stands for loss of four H+3,3 ', 5, 5' -biphenyltetracarboxylic acid) of formula C23H14N3O4Zn, crystal system is orthogonal, space group is Fddd, cell parameter
Figure BDA0002802896610000011
α ═ β ═ γ ═ 90 °; the zinc ion is in a penta-coordinated geometrical configuration, three nitrogen atoms are from 2,2':6', 2' -terpyridine, and two oxygen atoms are from 3,3 ', 5,5 ' -biphenyltetracarboxylic acid ligand.
The invention also provides a preparation method of the zinc complex with the porous structure, which comprises the following steps:
1) adding zinc acetate Zn (CH)3COO)2·2H2Placing O, 2', 6', 2' -terpyridine and 3,3 ', 5,5 ' -biphenyltetracarboxylic acid into a single-neck round-bottom flask according to the mass ratio of 3:2: 1;
2) adding a mixed solvent consisting of N, N-dimethylformamide and ethanol in a volume ratio of 1:1 into the single-neck round-bottom flask, stirring at normal temperature for 10-30 min, and transferring the mixture into a stainless steel reaction kettle;
3) putting the stainless steel reaction kettle into an oven, heating and reacting for 48-72 h at 110-130 ℃, naturally cooling to room temperature after the reaction is finished, and opening the stainless steel reaction kettle to obtain colorless blocky crystals;
4) testing and analyzing the obtained colorless bulk crystal by single crystal X-ray diffraction, wherein the structure shows that the molecular formula of the colorless bulk crystal is C23H14N3O4Zn, namely the zinc complex with the porous structure;
preferably, the substances participating in the reaction are all chemically pure.
Furthermore, the invention also provides the application of the zinc complex with the porous structure, and the complex is used as an adsorbing material for methane CH within ten minutes at standard atmospheric pressure4The adsorption capacity of the gas can reach 110cm3·g-1And the complex is used as an adsorbing material for more than 10 times in a circulating way, and the structure of the material can still be kept stable.
Compared with the prior art, the invention has the advantages that: the zinc complex has a porous structure (figure 1), has orderly pore channel arrangement, and can be applied to methane CH4Fields such as gas adsorption, catalyst support, chromatography, etc.; the complex molecular units have pi-pi stacking function, and the distance between the conjugated planes of 2,2':6', 2' -terpyridine is
Figure BDA0002802896610000021
(FIG. 2); the zinc complex takes zinc acetate as a source of metal ions, takes 3,3 ', 5,5 ' -biphenyltetracarboxylic acid ligand and 2,2', 6', 2' -terpyridine as organic ligands, adopts a solvothermal synthesis method to prepare the zinc complex porous material, and has the advantages of simple process and repeatabilityThe zinc complex three-dimensional ordered porous material has the advantages of good quality, high yield, mild synthesis conditions, low cost and easy large-scale production, so the zinc complex three-dimensional ordered porous material has wide application prospect in the fields of gas adsorption, ion exchange and the like.
Drawings
FIG. 1 is a porous structural view of a zinc complex of the present invention, with hydrogen atoms omitted for clarity;
FIG. 2 is a schematic representation of the pi-pi stacking interactions that exist between molecular units in the zinc complexes of the present invention, with hydrogen atoms omitted for clarity;
fig. 3 is a diagram showing the adsorption of methane gas by the zinc complex porous material of the present invention.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
Example 1:
weighing zinc acetate Zn (CH)3COO)2·2H2O (3.0mmol, 0.659g), 2,2':6', 2' -terpyridine (2.0mmol, 0.466g), 3,3 ', 5,5 ' -biphenyltetracarboxylic acid (1.0mmol, 0.330g) in a single-neck round-bottom flask, adding 20mL of N, N-dimethylformamide and 20mL of ethanol, stirring at normal temperature for 30min to obtain a reaction mixture solution, and then transferring the mixture to a stainless steel reaction kettle; and (2) putting the stainless steel reaction kettle into an oven, heating at 130 ℃ for reaction for 48 hours, naturally cooling to room temperature after the reaction is finished, and opening the stainless steel reaction kettle to obtain colorless blocky crystals, namely the zinc complex with the porous structure.
Example 2:
weighing Zn (CH)3COO)2·2H2O (0.3mmol, 0.0659g), 2,2':6', 2' -terpyridine (0.2mmol, 0.0466g), 3,3 ', 5,5 ' -biphenyltetracarboxylic acid (0.1mmol, 0.0330g) in a single-neck round-bottom flask, adding 10mL of N, N-dimethylformamide and 10mL of ethanol, stirring at room temperature for 10min to obtain a reaction mixture solution, and then transferring the mixture to a stainless steel reaction kettle; putting the stainless steel reaction kettle into an oven, heating at 110 ℃ for reaction for 72 hours, naturally cooling to room temperature after the reaction is finished, and opening the stainless steel reaction kettleThe steel reaction kettle obtains colorless blocky crystals, namely the zinc complex with the porous structure.
Example 3:
weighing Zn (CH)3COO)2·2H2O (3.0mmol, 0.659g), 2,2':6', 2' -terpyridine (2.0mmol, 0.466g), 3,3 ', 5,5 ' -biphenyltetracarboxylic acid (1.0mmol, 0.330g) in a single-neck round-bottom flask, adding 20mL of N, N-dimethylformamide and 20mL of ethanol, stirring at normal temperature for 20min to obtain a reaction mixture solution, and then transferring the mixture to a stainless steel reaction kettle; and (2) putting the stainless steel reaction kettle into an oven, heating at 120 ℃ for reaction for 60 hours, naturally cooling to room temperature after the reaction is finished, and opening the stainless steel reaction kettle to obtain colorless blocky crystals, namely the zinc complex with the porous structure.
Taking the colorless bulk crystal obtained in example 3 as an example, single crystal X-ray diffraction test analysis was performed. It should be noted that the colorless bulk crystals prepared in the other examples have the same crystal structure. The test analysis shows that the molecular formula of the colorless blocky crystal is C23H14N3O4Zn, crystal system is orthogonal, space group is Fddd, cell parameter
Figure BDA0002802896610000031
Figure BDA0002802896610000032
α ═ β ═ γ ═ 90 °; the zinc ion is in a penta-coordinate geometrical configuration, three nitrogen atoms are from 2,2':6', 2' -terpyridine, two oxygen atoms are from 3,3 ', 5,5 ' -biphenyl tetracarboxylic acid ligand, and the zinc ion is the zinc complex with the porous structure. The space accumulation of the structural units of the complex presents a porous structure (figure 1); pi-pi stacking exists among molecular units in the complex, as shown in FIG. 2.
The use of the complex prepared in this application is illustrated by way of example of the complex prepared in example 3. The other experimental examples had similar effects. The complex is used as an adsorbing material, and methane is generated in ten minutes under the standard atmospheric pressureCH4The adsorption capacity of the gas is more than or equal to 110cm3·g-1(figure 3), the adsorption and desorption can be recycled for more than 10 times, and the structure of the material can still be kept stable.
Zn(CH3COO)2·2H2O, molecular weight 219.50;
2,2', 6', 2' -terpyridine, formula C15H11N3Molecular weight: 233.26794, respectively;
3,3 ', 5, 5' -biphenyltetracarboxylic acid of the formula C16H10O8Molecular weight 330.2458.

Claims (3)

1. A zinc complex with a porous structure, characterized in that the zinc complex is an organic-inorganic hybrid coordination compound containing zinc and 3,3 ', 5,5 ' -biphenyltetracarboxylic acid and 2,2':6', 2' -terpyridine ligands, having the structural formula [ Zn (tpy) (L)0.5]Tpy stands for 2,2':6', 2' -terpyridine, L stands for loss of four H+3,3 ', 5, 5' -biphenyltetracarboxylic acid of formula C23H14N3O4Zn, crystal system is orthogonal, space group is Fddd, cell parameter
Figure FDA0002802896600000011
Figure FDA0002802896600000012
α ═ β ═ γ ═ 90 °; the zinc ion is in a penta-coordinated geometrical configuration, three nitrogen atoms are from 2,2':6', 2' -terpyridine, and two oxygen atoms are from 3,3 ', 5,5 ' -biphenyltetracarboxylic acid ligand.
2. A method for preparing a zinc complex having a porous structure according to claim 1, comprising the steps of:
1) adding zinc acetate Zn (CH)3COO)2·2H2Placing O, 2', 6', 2' -terpyridine and 3,3 ', 5,5 ' -biphenyltetracarboxylic acid into a single-neck round-bottom flask according to the mass ratio of 3:2: 1;
2) adding a mixed solvent consisting of N, N-dimethylformamide and ethanol in a volume ratio of 1:1 into the single-neck round-bottom flask, stirring at normal temperature for 10-30 min, and transferring the mixture into a stainless steel reaction kettle;
3) putting the stainless steel reaction kettle into an oven, heating and reacting for 48-72 h at 110-130 ℃, naturally cooling to room temperature after the reaction is finished, and opening the stainless steel reaction kettle to obtain colorless blocky crystals;
4) and testing and analyzing the obtained colorless bulk crystal by single crystal X-ray diffraction, and displaying the structure of the colorless bulk crystal as the zinc complex with the porous structure.
3. Use of a zinc complex having a porous structure according to claim 1, wherein the zinc complex is used as an adsorbing material, and the methane gas adsorption capacity is 110cm or more at a standard atmospheric pressure within ten minutes3·g-1And the adsorption and desorption can be recycled for more than 10 times, and the structure of the material can still be kept stable.
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