CN111333851A - Normal-pressure preparation method of zirconium metal-organic framework material UIO-66 - Google Patents
Normal-pressure preparation method of zirconium metal-organic framework material UIO-66 Download PDFInfo
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Abstract
The invention relates to a normal pressure preparation method of a zirconium metal-organic framework material UIO-66. Dissolving a zirconium source and an organic ligand in a solvent according to a molar ratio of 0.7-1.4: 1 to prepare a reactant solution; placing the dissolved solution in a container connected with a reflux device, heating and stirring for reaction to obtain a UIO-66 material, wherein the heating temperature is 100-150 ℃, the stirring speed is 50-700 r/min, and the reaction time is 3-20 h; centrifugally separating the obtained UIO-66 material, washing with methanol, and soaking; and finally, drying the solid in a vacuum drying oven at the temperature of 30-200 ℃ to obtain the composite material. The invention improves the solvent thermal synthesis step and equipment, changes standing into stirring and changes closed high pressure into communication with the atmosphere, shortens the reaction time, improves the yield from 54 percent to 78 percent and ensures safe reaction process; the synthesized UIO-66 has uniform granularity, small grain diameter and good dispersibility.
Description
Technical Field
The invention relates to the field of preparation of metal-organic framework materials, in particular to a normal-pressure preparation method of a zirconium metal-organic framework material UIO-66.
Background
A Metal-Organic Framework (MOF) is a porous material with a three-dimensional periodic network structure formed by self-assembly of Organic ligands and Metal centers. The catalyst has the advantages of adjustable structure, permanent porosity, ultrahigh specific surface area, easy chemical modification and functionalization and the like, and has wide application prospect in a plurality of research fields of gas storage, separation, catalysis, sensing and the like.
The UO-66 (UO) series organic Metal framework (MOF) is a Metal framework (MOF) with Zr as the Metal center and 1, 4-terephthalic acid (H)2BDC) and derivatives thereof as organic ligands was first reported in 2008 by the Cavka research group at the university of oslo, norwegian. UiO-66 is composed of regular octahedron Zr6O4(OH)4Metal cluster and H2The BDC is formed by complexing, and the structure of the BDC contains two kinds of hole cages which are shaped like a regular octahedron and a regular tetrahedron and are connected with each other through a triangular hole window. UiO-66 has several unique advantages over other MOF materials as follows. Firstly, UIO-66 has excellent hydrothermal stability and chemical stability, and can still keep the stability of the crystal structure at high temperature up to 500 ℃. Furthermore, Ui0-66 is structurally stable in water, conventional organic solvents such as N, N-dimethylformamide, benzene or acetone. Secondly, the MOF also has better mechanical stability, and the framework structure can bear the mechanical pressure of up to 1 MPa. The UiO-66 also has strong acid resistance and certain alkali resistance, and the application potential of the MOF in some extreme environments is greatly expanded. In addition, coordination defects exist in the actual structure of the UiO-66, namely, a part of metal nodes are in an incomplete coordination state, on one hand, the defects can greatly influence the specific surface area of the UiO-66, for example, the specific surface area of the synthesized UiO-66 under different conditions is generally 600-1600 m2g-1Within the range. On the other hand, the zirconium metal sites with incomplete coordination can be used as metal reaction catalytic centers, so that the unique properties of the MOFs are endowed. These unique properties possessed by UiO-66 have led to its birth and interest in catalysis, gases and particularly CO2The potential application in the fields of adsorption storage, sewage treatment and the like is deeply explored.
Currently, the synthesis method of UIO-66 is generally based on a solvothermal method, and comprises the steps of dissolving zirconium chloride and terephthalic acid in N, N-dimethylformamide, transferring the solution into a stainless steel reaction kettle with polytetrafluoroethylene, heating the reaction kettle to the temperature of 100 ℃ and 150 ℃ by using an oven, standing for reaction for 24 hours, and then filtering, washing and drying to obtain powdery solid, namely UIO-66. However, the preparation of UIO-66 requires a growth process, wherein small grains are generated first, then large grains are gradually generated, and finally the grains tend to be stable. The method can not stir, the UIO-66 generated firstly in the standing process is precipitated at the bottom of the reaction kettle, so that a reaction system is not uniform, the particle size of the prepared UIO-66 is not uniform, the requirements on equipment are high (high pressure resistance and corrosion resistance), the safety performance is poor, the yield is low, and mass production cannot be realized. Therefore, how to prepare UIO-66 efficiently, safely and in large batch is an urgent problem to be solved in practical application.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides the following technical scheme.
An atmospheric pressure preparation method of a zirconium metal-organic framework material UIO-66 comprises the following steps:
(1) dissolving a zirconium source and an organic ligand in a solvent according to a molar ratio of 0.7-1.4: 1 to prepare a reactant solution;
(2) placing the dissolved solution in a container connected with a reflux device, heating and stirring for reaction to obtain a UIO-66 material, wherein the heating temperature is 100-150 ℃, the stirring speed is 50-700 r/min, and the reaction time is 3-20 h;
(3) centrifugally separating the obtained UIO-66 material, washing with methanol, and soaking;
(4) and finally, drying the solid in a vacuum drying oven at the temperature of 30-200 ℃ to obtain the composite material.
The solvent is a mixed solution of a regulator and N, N-dimethylformamide, wherein the content of the regulator in the mixed solution is 0.001-10 mol/L.
The concentration of Zr4+ in the reactant solution is 0.001-1 mol/L, and the concentration of the organic ligand is 0.001-1 mol/L.
The zirconium source comprises zirconium oxychloride, zirconium n-propoxide or zirconium tetrachloride.
The organic ligand comprises terephthalic acid and derivatives thereof, including 2-amino terephthalic acid, 2-hydroxy terephthalic acid, 2-bromo terephthalic acid, 2-nitro terephthalic acid, 1, 2, 4-benzene tricarboxylic acid, 2, 5-diamino terephthalic acid, 2, 5-dihydroxy terephthalic acid or 1, 2, 4, 5-benzene tetracarboxylic acid.
The regulator comprises monocarboxylic compounds or halogen hydride.
The regulator comprises benzoic acid, formic acid, acetic acid, trifluoroacetic acid, HCl, HF or water.
The reflux device assembled on the reaction container is directly communicated with the atmospheric environment, and the whole system is under the atmospheric pressure.
The invention dissolves a zirconium source and an organic ligand in a solvent, and the UIO-66 material is synthesized by heating and stirring under normal pressure. The invention improves the solvent thermal synthesis step and equipment, changes standing into stirring and changes closed high pressure into communication with the atmosphere, thereby ensuring uniform reaction system and safe reaction process in the reaction process; the synthesized UIO-66 has uniform granularity, small grain diameter and good dispersibility.
The method greatly improves the utilization rate of reactants, improves the yield from 54 percent to 78 percent, shortens the reaction time, has simple operation, low requirement on reaction equipment and mild condition, and is expected to be used for the mass preparation of UIO-66 series MOF. The invention can efficiently synthesize the monodisperse UIO-66 material with good uniformity.
Drawings
FIG. 1 is a scanning electron micrograph of UIO-66 prepared in example 1
FIG. 2 is a powder X-ray diffraction pattern of UIO-66 prepared in example 1
FIG. 3 is a graphical representation of the UIO-66 nitrogen adsorption desorption profile produced in example 1
FIG. 4 is a UIO-66 pore size distribution plot prepared in example 1
FIG. 5 is a schematic view of a reaction apparatus
Detailed Description
The invention relates to a method for preparing a zirconium metal-organic framework material UIO-66, which comprises the following steps:
(1) dissolving a zirconium source and an organic ligand in a solvent according to a molar ratio of 0.7-1.4: 1 to prepare a reactant solution;
(2) placing the dissolved solution in a container connected with a reflux device, heating and stirring for reaction to obtain a UIO-66 material, wherein the heating temperature is 100-150 ℃, the stirring speed is 50-700 r/min, and the reaction time is 3-20 h;
(3) centrifugally separating the obtained UIO-66 material, washing with methanol, and soaking;
(4) finally, putting the solid in a vacuum drying oven at 30-200 ℃ for vacuum drying to obtain the product
The solvent is a mixed solution of a regulator and N, N-dimethylformamide, wherein the concentration of the regulator is 0.001-10 mol/L; the concentration of Zr4+ in the reactant solution is 0.001-1 mol/L, and the concentration of the organic ligand is 0.001-1 mol/L.
The zirconium source comprises zirconium oxychloride, zirconium n-propoxide, zirconium tetrachloride and the like.
The organic ligands include terephthalic acid and its derivatives (e.g., 2-aminoterephthalic acid, 2-hydroxyterephthalic acid, 2-bromoterephthalic acid, 2-nitroterephthalic acid, 1, 2, 4-benzenetricarboxylic acid, 2, 5-diaminoterephthalic acid, 2, 5-dihydroxyterephthalic acid, 1, 2, 4, 5-benzenetetracarboxylic acid, etc.).
The regulator comprises monocarboxylic compounds (such as benzoic acid, formic acid, acetic acid, trifluoroacetic acid), halogen hydride (such as HCl, HF), water and the like.
The following examples are provided to further illustrate the invention
Example 1
Dissolving zirconium chloride and 2-amino terephthalic acid in a solvent according to a molar ratio of 1:1 to prepare a reactant solution; placing the dissolved solution in a container connected with a reflux device, heating and stirring for reaction, wherein the heating temperature is 120 ℃, the stirring speed is 400r/min, and the reaction time is 12 h; after the reaction is stopped, centrifugally separating, washing with methanol and soaking; finally, the solid is placed in a vacuum drying box at 60 ℃ for vacuum drying to obtain the UIO-66 material.
The solvent is a mixed solution of acetic acid and N, N-dimethylformamide, wherein the concentration of the acetic acid is 2.4 mol/L; the concentration of Zr4+ in the reactant solution was 0.008mol/L and the concentration of 2-aminoterephthalic acid was 0.008 mol/L.
Using the product of this example as an example, 522.6mg of UIO-66 material was obtained in 78% yield; FIG. 1 is a scanning electron micrograph of the obtained UIO-66, which shows that the obtained UIO-66 is an octahedral particle with regular crystal planes and uniform particle size. FIG. 2 is an X-ray diffraction pattern of the obtained UIO-66, from which it can be seen that the obtained UIO-66 has a distinct crystal structure. FIG. 3 shows N of the obtained UIO-662The adsorption-desorption curve revealed that the BET comparative area of the obtained UIO-66 was 1115m2(ii) in terms of/g. FIG. 4 is a graph showing the pore size distribution of the obtained UIO-66, from which it can be seen that the pore size of the obtained UIO-66 was 0.48 nm.
Example 2
Dissolving zirconium oxychloride and terephthalic acid in a solvent according to a molar ratio of 1:1 to prepare a reactant solution; placing the dissolved solution in a container connected with a reflux device, heating and stirring for reaction, wherein the heating temperature is 150 ℃, the stirring speed is 700r/min, and the reaction time is 3 h; after the reaction is stopped, centrifugally separating, washing with methanol and soaking; finally, the solid is placed in a vacuum drying box at 30 ℃ for vacuum drying to obtain the UIO-66 material.
The solvent is a mixed solution of acetic acid and N, N-dimethylformamide, wherein the concentration of the acetic acid is 0.001 mol/L; the concentration of Zr4+ in the reactant solution was 1mol/L, and the concentration of terephthalic acid was 0.008 mol/L.
Example 3
Dissolving zirconium n-propoxide and p-2-bromobenzoic acid in a solvent according to a molar ratio of 1:1 to prepare a reactant solution; placing the dissolved solution in a container connected with a reflux device, heating and stirring for reaction, wherein the heating temperature is 100 ℃, the stirring speed is 50r/min, and the reaction time is 20 h; after the reaction is stopped, centrifugally separating, washing with methanol and soaking; and finally, putting the solid in a vacuum drying oven at 200 ℃ for vacuum drying to obtain the UIO-66 material.
The solvent is a mixed solution of formic acid and N, N-dimethylformamide, wherein the concentration of the formic acid is 10 mol/L; the concentration of Zr4+ in the reactant solution is 1mol/L, and the concentration of p-2-bromobenzoic acid is 1 mol/L.
Example 4
Dissolving zirconium chloride and p-2-nitrobenzoic acid in a solvent according to a molar ratio of 0.7:1 to prepare a reactant solution; placing the dissolved solution in a container connected with a reflux device, heating and stirring for reaction, wherein the heating temperature is 120 ℃, the stirring speed is 4000r/min, and the reaction time is 12 h; after the reaction is stopped, centrifugally separating, washing with methanol and soaking; and finally, putting the solid in a vacuum drying oven at 100 ℃ for vacuum drying to obtain the UIO-66 material.
The solvent is a mixed solution of HCl and N, N-dimethylformamide, wherein the concentration of HCl is 10 mol/L; the concentration of Zr4+ in the reactant solution was 0.07mol/L, and the concentration of p-2-nitroterephthalic acid was 0.1 mol/L.
Example 5
Dissolving zirconium chloride and 2, 5-diaminoterephthalic acid in a solvent according to a molar ratio of 1.4:1 to prepare a reactant solution; placing the dissolved solution in a container connected with a reflux device, heating and stirring for reaction, wherein the heating temperature is 120 ℃, the stirring speed is 400r/min, and the reaction time is 20 h; after the reaction is stopped, centrifugally separating, washing with methanol and soaking; finally, the solid is placed in a vacuum drying box at 30 ℃ for vacuum drying to obtain the UIO-66 material.
The solvent is a mixed solution of benzoic acid and N, N-dimethylformamide, wherein the concentration of the benzoic acid is 3.6 mol/L; the concentration of Zr4+ in the reactant solution was 0.14mol/L, and the concentration of 2, 5-diaminoterephthalic acid was 0.1 mol/L.
Example 6
Dissolving zirconium chloride and 2, 5-dihydroxyterephthalic acid in a solvent according to a molar ratio of 1:1 to prepare a reactant solution; placing the dissolved solution in a container connected with a reflux device, heating and stirring for reaction, wherein the heating temperature is 120 ℃, the stirring speed is 400r/min, and the reaction time is 20 h; after the reaction is stopped, centrifugally separating, washing with methanol and soaking; and finally, putting the solid in a vacuum drying box at 90 ℃ for vacuum drying to obtain the UIO-66 material.
The solvent is a mixed solution of benzoic acid and N, N-dimethylformamide, wherein the concentration of the benzoic acid is 3.6 mol/L; the concentration of Zr4+ in the reactant solution was 0.01mol/L, and the concentration of 2, 5-dihydroxyterephthalic acid was 0.01 mol/L.
Example 7
Dissolving zirconium chloride and 1, 2, 4-benzene tricarboxylic acid in a solvent according to a molar ratio of 1:1 to prepare a reactant solution; placing the dissolved solution in a container connected with a reflux device, heating and stirring for reaction, wherein the heating temperature is 120 ℃, the stirring speed is 400r/min, and the reaction time is 20 h; after the reaction is stopped, centrifugally separating, washing with methanol and soaking; and finally, putting the solid in a vacuum drying box at 90 ℃ for vacuum drying to obtain the UIO-66 material.
The solvent is a mixed solution of trifluoroacetic acid and N, N-dimethylformamide, wherein the concentration of the trifluoroacetic acid is 3.6 mol/L; the concentration of Zr4+ in the reactant solution is 0.08mol/L, and the concentration of 1, 2, 4-benzenetricarboxylic acid is 0.08 mol/L.
Example 8
Dissolving zirconium chloride and 1, 2, 4, 5-benzenetetracarboxylic acid in a solvent according to a molar ratio of 1:1 to prepare a reactant solution; placing the dissolved solution in a container connected with a reflux device, heating and stirring for reaction, wherein the heating temperature is 120 ℃, the stirring speed is 400r/min, and the reaction time is 20 h; after the reaction is stopped, centrifugally separating, washing with methanol and soaking; and finally, putting the solid in a vacuum drying box at 90 ℃ for vacuum drying to obtain the UIO-66 material.
The solvent is a mixed solution of HF and N, N-dimethylformamide, wherein the concentration of HF is 3.6 mol/L; the concentration of Zr4+ in the reactant solution was 0.08mol/L, and the concentration of 1, 2, 4, 5-benzenetetracarboxylic acid was 0.08 mol/L.
Example 9
Dissolving zirconium chloride and 2-hydroxy terephthalic acid in a solvent according to a molar ratio of 1:1 to prepare a reactant solution; placing the dissolved solution in a container connected with a reflux device, heating and stirring for reaction, wherein the heating temperature is 120 ℃, the stirring speed is 400r/min, and the reaction time is 20 h; after the reaction is stopped, centrifugally separating, washing with methanol and soaking; and finally, putting the solid in a vacuum drying box at 90 ℃ for vacuum drying to obtain the UIO-66 material.
The solvent is a mixed solution of water and N, N-dimethylformamide, wherein the concentration of water is 6 mol/L; the concentration of Zr4+ in the reactant solution was 0.08mol/L, and the concentration of 2-hydroxyterephthalic acid was 0.08 mol/L.
Claims (8)
1. A normal pressure preparation method of a zirconium metal-organic framework material UIO-66 is characterized by comprising the following steps:
(1) dissolving a zirconium source and an organic ligand in a solvent according to a molar ratio of 0.7-1.4: 1 to prepare a reactant solution;
(2) placing the dissolved solution in a container connected with a reflux device, heating and stirring for reaction to obtain a UIO-66 material, wherein the heating temperature is 100-150 ℃, the stirring speed is 50-700 r/min, and the reaction time is 3-20 h;
(3) centrifugally separating the obtained UIO-66 material, washing with methanol, and soaking;
(4) and finally, drying the solid in a vacuum drying oven at the temperature of 30-200 ℃ to obtain the composite material.
2. The method as set forth in claim 1, wherein the solvent is a mixed solution of a conditioning agent and N, N-dimethylformamide, and wherein the concentration of the conditioning agent in the mixed solution is 0.001mol/L to 10 mol/L.
3. The method as set forth in claim 1, wherein the reactant solution contains Zr4+ in a concentration of 0.001mol/L to 1mol/L and the organic ligand in a concentration of 0.001mol/L to 1 mol/L.
4. The method of claim 1, wherein the zirconium source comprises zirconium oxychloride, zirconium n-propoxide, or zirconium tetrachloride.
5. The process of claim 1 wherein the organic ligand comprises terephthalic acid and derivatives thereof, including 2-aminoterephthalic acid, 2-hydroxyterephthalic acid, 2-bromoterephthalic acid, 2-nitroterephthalic acid, 1, 2, 4-benzenetricarboxylic acid, 2, 5-diaminoterephthalic acid, 2, 5-dihydroxyterephthalic acid or 1, 2, 4, 5-benzenetetracarboxylic acid.
6. The method of claim 1, wherein the modifier comprises a monocarboxylic acid compound or a halogen hydride.
7. The method of claim 1, wherein the modifier comprises benzoic acid, formic acid, acetic acid, trifluoroacetic acid, HCl, HF, or water.
8. The method of claim 1, wherein the reaction vessel is equipped with a reflux unit that is directly open to the atmosphere and the entire system is at ambient atmospheric pressure.
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