CN114316291A - Metal-organic framework based on trispyrazole ligand, preparation method and application of metal-organic framework in organic dye degradation - Google Patents
Metal-organic framework based on trispyrazole ligand, preparation method and application of metal-organic framework in organic dye degradation Download PDFInfo
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Abstract
The invention discloses a metal-organic framework based on a tri-pyrazole ligand, a preparation method and application thereof in organic dye degradation, and belongs to the technical field of crystalline materials. The chemical formula of the metal-organic framework [ Zn ]7(OH)2(TPA)4(H2O)]The organic ligand is 4,4',4' -tri (1H-pyrazol-4-yl) triphenylamine (H)3TPA). The preparation method is that under the sealed condition, the organic ligand H3TPA, zinc nitrate hexahydrate and 4,4' -bipyridine inN,N-crystals of such metal-organic frameworks are obtained via thermal reaction in a mixed solution of dimethylformamide and water. The metal-organic framework material has a large specific surface area and a permanent pore structure, and can maintain the integrity of the framework structure in an aqueous solution environment with the pH value of 2-13. The material has visible light absorption performance, and can be used in water bodyA catalyst for photocatalytic degradation of organic dyes.
Description
Technical Field
The invention belongs to the technical field of crystalline materials, and relates to a metal-organic coordination polymer material, in particular to a metal-organic framework based on a tri-pyrazole ligand, a preparation method and application thereof in organic dye degradation.
Background
Metal-organic frameworks (MOFs) are hybrid crystalline materials formed by self-assembly of organic ligands and metal nodes, and have the characteristics of both organic and inorganic materials. Meanwhile, the catalyst has the characteristics of designable structure, tailorable property, high specific surface area and the like, is widely concerned in the application fields of gas adsorption and separation, catalysis, sensing, electrochemistry and the like, and the industrial application is gradually promoted. The dye is an indispensable material in the industrial production processes of plastics, textiles, paper making, leather and the like, and the produced dye wastewater causes serious pollution problems to the ecological environment. In addition, most dyes are synthetic organic dyes containing aromatic rings, which have potential carcinogenicity and mutagenicity to organisms. The novel catalyst material is developed, organic molecules are degraded through photocatalysis to remove pollution of organic dyes in water, and the method is a green application technology and has excellent marketization application prospect. The hybrid properties and structural designability of the metal-organic framework make it a very promising photocatalyst material. After decades of efforts, the metal-organic framework material has made a great progress in designing and developing the photocatalyst.
Stability is a key challenge in the practical application of metal-organic framework materials, especially in application systems facing water environments. For the preparation of metal-organic framework photocatalysts, the introduction of photon absorption groups and the construction of catalytic active centers are two core problems of the technology. The metal-organic framework material obtained by the invention has excellent water system stability, and through organic ligand molecule design, the metal-organic framework material can absorb visible light and excite an active center to degrade organic dye molecules in water. Therefore, the material has potential application value in removing organic dye pollutants in water.
Disclosure of Invention
The invention aims to provide a metal-organic framework based on a tri-pyrazole ligand, a preparation method and application thereof in organic dye degradation.
The invention is based on a tri-pyrazole ligand metal-organic framework with a chemical formula of [ Zn ]7(OH)2(TPA)4(H2O)]Wherein the metal node is zinc (Zn)2+) Ionic, TPA3−Is a deprotonated photoactive organic ligand 4,4',4' -tris (1H-pyrazol-4-yl) triphenylamine (CAS number: 2172856-38-9). The crystal material is synthesized by a dissolution thermal synthesis method, and the structure of the crystal material is analyzed by single crystal diffraction. The crystal is a three-dimensional metal-organic framework material, the crystal structure belongs to a monoclinic system, and the space group isC2/cThe unit cell parameters are:a =37.767(3) Å， b =15.9977(13) Å，c =32.703(3) Å；α =90 °，β =111.374(5) °，γ =90 °。
in the three-dimensional metal-organic framework, there are four crystallographically independent Zn2+Ions (Zn 1-4) all connect four coordinating atoms in a tetrahedral coordination mode. Wherein the four atoms coordinated to Zn1 and Zn2 are 4N atoms from four different TPA ligand pyrazole groups; the four atoms coordinated to Zn3 are 3N atoms and 1 from three different TPA ligand pyrazole groupsμ 2-OH; and the four atoms coordinated to Zn4 are derived from 2N atoms, 1-OH and 1H of two different TPA ligand pyrazole groups2And O. Ligand H in the Complex Structure3Total removal of 3H protons of TPA, TPA3−Pyrazole radicals of ligands orμ 2-η 1:η 1The coordination mode of (a) bridges the metal nodes. Pyrazole radicals andμ 2the-OH groups bridging adjacent Zn2+Ions, forming one-dimensional metal chains along the crystallographic (101) direction. TPA3−The ligands bridge adjacent metal chains to form a three-dimensional framework with one-dimensional channels along the crystallographic (101) direction.
The porosity of the three-dimensional metal-organic framework, accessible to the whole framework after removal of the solvent molecules, was 58.5%. The specific surface area calculated from the nitrogen adsorption curve at a temperature of 77K was 1659 m2 g−1The pore diameter is distributed in the range of 8-12 anga. More importantly, the material has excellent stability. And soaking in an aqueous solution with the pH value of 2-13 for 24 hours at room temperature, wherein the frame structure and the porosity of the material can be kept complete. As described above, the metal-organic framework has permanent pores, suitable pore size and Zn metal node coordinated end groups-OH and H2O, making it suitable for adsorption and catalytic applications.
Wherein the organic ligand 4,4',4' -tri (1H-pyrazol-4-yl) triphenylamine (H)3TPA) has the chemical structural formula
The invention relates to a preparation method of a metal-organic framework based on a tri-pyrazole ligand, which comprises the following steps:
under sealed conditions, organic ligand H3TPA with a metal salt Zn (NO)3)2·6H2O and 4,4' -bipyridine in DMF (N, N-dimethylformamide) and water to obtain [ Zn ] through thermal reaction7(OH)2(TPA)4(H2O)]A crystalline material. It is noted that the role of 4,4' -bipyridine in the crystal synthesis process is as a solvent acidity regulator and a templating agent.
Wherein, the organic ligand H3TPA and Zn (NO)3)2·6H2The molar ratio of O is 1 (1.5-4), and each 0.1 mmol of H3TPA corresponds to 0.3-0.8 mmol of 4,4' -bipyridine and 8-15 mL of DMF, and the proportion range of the mixed solution is DMF: H2O = 4 (0.5-1.2). The temperature of the solvothermal reaction is 90-120 ℃, and the reaction time is 24-48 hours.
The invention has the beneficial effects that:
the metal-organic framework based on the tri-pyrazole ligand has a novel structure and stable framework, and has potential application in photocatalytic degradation of organic dyes in water. The metal-organic framework material based on the tri-pyrazole ligand has a remarkable photocatalytic degradation effect on methylene blue, Congo red and methyl violet, and can be applied to efficient treatment of organic pollutants in water, namely the methylene blue, the Congo red and the methyl violet. The preparation method has simple process, easy implementation and high yield, and is beneficial to large-scale popularization.
Drawings
FIG. 1 is a Zn-pyrazole metal chain diagram of the metal-organic framework.
Fig. 2 is a three-dimensional frame diagram of the metal-organic frame.
FIG. 3 is a 77K nitrogen sorption isotherm plot and pore size distribution plot for the metal-organic framework.
FIG. 4 is a powder diffraction pattern of the metal-organic framework after treatment with aqueous solutions of different pH.
FIG. 5 is a solid state UV absorption spectrum of the metal organic framework.
FIG. 6 is a graph showing the efficiency of photocatalytic degradation of organic dyes methylene blue, Congo red and methyl violet by the metal-organic framework material.
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
Organic ligand H3TPA (0.1 mmol), 4,4' -bipyridine (0.3 mmol) was dissolved in 8 ml DMF by sonication, Zn (NO)3)2·6H2O (0.2 mmol) was dissolved in 1.0 ml of deionized water, and the two were mixed and sealed in a glass bottle. Crystals of the metal-organic framework were obtained via a thermal reaction at 120 ℃ for 48 hours.
Example 2
Organic ligand H3TPA (0.1 mmol), 4,4' -bipyridine (0.8 mmol) was dissolved in 8 ml DMF by sonication, Zn (NO)3)2·6H2O (0.4 mmol) was dissolved in 2.4 ml of deionized water, and the two were mixed and sealed in a glass bottle. Obtained by thermal reaction at 120 ℃ for 36 hoursCrystals of the metal-organic framework.
Example 3
Organic ligand H3TPA (0.04 mmol), 4,4' -bipyridine (0.12 mmol) was dissolved in 4 ml DMF by sonication, Zn (NO)3)2·6H2O (0.16 mmol) was dissolved in 1.0 ml of deionized water, and the two were mixed and sealed in a glass bottle. The crystals of the metal-organic framework were obtained via a thermal reaction at 120 ℃ for 36 hours.
Example 4
Organic ligand H3TPA (0.04 mmol), 4,4' -bipyridine (0.32 mmol) was dissolved in 6 ml DMF by sonication, Zn (NO)3)2·6H2O (0.16 mmol) was dissolved in 1.0 ml of deionized water, and the two were mixed and sealed in a glass bottle. The crystals of the metal-organic framework were obtained via a thermal reaction at 100 ℃ for 36 hours.
Example 5
Organic ligand H3TPA (0.02 mmol), 4,4' -bipyridine (0.06 mmol) was dissolved in 2 ml DMF by sonication, Zn (NO)3)2·6H2O (0.03 mmol) was dissolved in 0.25 ml of deionized water, and the two were mixed and sealed in a glass bottle. Crystals of the metal-organic framework were obtained via a thermal reaction at 90 ℃ for 54 hours.
Example 6
Organic ligand H3TPA (0.02 mmol), 4,4' -bipyridine (0.16 mmol) was dissolved in 2 ml DMF by sonication, Zn (NO)3)2·6H2O (0.04 mmol) was dissolved in 0.25 ml of deionized water, and the two were mixed and sealed in a glass bottle. The crystals of the metal-organic framework were obtained via a thermal reaction at 100 ℃ for 36 hours.
The test results of the products obtained in the above examples are the same, and specifically the following are given:
(1) and (3) crystal structure determination:
single crystals of appropriate size were selected under a microscope and data collected using an Agilent Technologies SuperNova single crystal diffractometer at a temperature of 296K. Data were collected and restored using CrysAlisPro software. The crystal structure was resolved by direct method using the program SHELXTL-2019. Firstly, determining all non-hydrogen atom coordinates by using a difference function method and a least square method, obtaining hydrogen atom positions by using a theoretical hydrogenation method, and then refining the crystal structure by using SHELXTL-2019. The block diagrams are shown in fig. 1 and fig. 2. The crystallographic data are shown in table 1.
TABLE 1 crystallography data for metal organic framework materials
The block diagram of fig. 1 shows: the metal-organic framework comprises pyrazole-metal zinc chains. Wherein the zinc ions are coordinated in a tetrahedral coordination mode and four N/O atoms. Adjacent zinc ion andμ 2the-OH groups and the deprotonated pyrazole groups are alternately connected to form a one-dimensional pyrazole-metal zinc chain.
The block diagram of fig. 2 shows: in the three-dimensional metal-organic framework, one-dimensional pore channels with rhombic sections exist along the direction of crystallography (101).
(2) Characterization of pore properties
FIG. 3 shows the material of the present inventionP/P 0 Nitrogen adsorption isotherms under the conditions of = 1 and 77K. As can be seen from the figure, the maximum N of the metal-organic framework2The adsorption capacity is 521.18 cm3 g-1The BET specific surface area calculated therefrom was 1659 m2g-1。
(3) Characterization of stability
FIG. 4 is a powder diffraction pattern of the inventive material after treatment with aqueous solutions of different pH. As can be seen from the figure, after the material is treated in an aqueous solution with the pH value of 2-13 for 24 hours, the diffraction peak is not significantly changed compared with the originally synthesized material, and the framework structure of the crystal material can be kept intact in the aqueous solution environment.
(3) The performance characterization of the photocatalytic degradation organic dye:
FIG. 6 is a graph showing the efficiency of photocatalytic degradation of methylene blue, Congo red and methyl violet by the material of the present invention. Reaction conditions are as follows: the illumination wavelength range is 200 nm-800 nm; the reaction system is 50 ml 20 mg L−1And 10 mg of metal-organic framework material; the reaction temperature was 25 ℃. As can be seen from the figure, after the visible light is irradiated for 4 hours, the degradation rates of the material on methylene blue, Congo red and methyl violet reach 95.1%, 90.0% and 72.6%, respectively. The material has obvious photocatalytic degradation effect on methylene blue, Congo red and methyl violet under the condition, and can be applied to efficient treatment of organic pollutants in water, namely the methylene blue, the Congo red and the methyl violet.
Claims (7)
1. A metal-organic framework based on a tripyrazole ligand characterized by the chemical formula [ Zn ]7(OH)2(TPA)4(H2O)]TPA is an organic ligand for removing H proton, namely 4,4',4' -tri (1H-pyrazol-4-yl) triphenylamine.
2. The metal-organic framework based on the tri-pyrazole ligand as claimed in claim 1, wherein the crystal structure of the metal-organic framework material of the tri-pyrazole ligand belongs to the monoclinic system and the space group isC2/c，The unit cell parameters are:a =37.767(3) Å，b =15.9977(13) Å，c =32.703(3) Å；α =90 °，β =111.374(5) °，γ =90 °。
3. the metal-organic framework based on trispyrazole ligands according to claim 2, characterized in that there are four crystallographically independent metallic Zn in the three-dimensional metal-organic framework2+Ions of these metals with N atoms from different ligands and-OH/H in a tetrahedral coordination mode2Coordination of O atom of O; ligand H in the Complex Structure3Three H protons of TPA are totally removed from TPA3− Pyrazole radicals of ligands andμ 2the-OH groups bridging adjacent Zn2+The ions form a zinc metal chain; TPA3−The ligand and the zinc metal chain are alternately connected to form a three-dimensional porous framework.
4. The metal-organic framework based on trispyrazole ligands according to claim 3, characterized in that the three-dimensional metal-organic framework presents rhombohedral one-dimensional channels along the crystallographic (101) direction.
5. A process for the preparation of a metal-organic framework based on a trispyrazole ligand according to any of claims 1 to 4, comprising the following steps:
organic ligand 4,4',4' -tri (1H-pyrazol-4-yl) triphenylamine (H) under sealed condition3TPA）、Zn(NO3)2·6H2O and 4,4' -bipyridine in DMF (N, N-dimethylformamide) and water to obtain [ Zn ] through thermal reaction7(OH)2(TPA)4(H2O)]Metal-organic framework materials.
6. The method of claim 5, wherein the organic ligand 4,4',4' -tris (1H-pyrazol-4-yl) triphenylamine (H) is selected from the group consisting of3TPA) with Zn (NO)3)2·6H2The molar ratio of O is 1 (1.5-4), and each 0.1 millimole of H3TPA corresponding to 0.3-0.8 mmol of 4,4' -bipyridine and 8-15 ml of TPAN, NDimethylformamide (DMF), the ratio of the mixed solution being in the range of DMF: H2O = 4 (0.5-1.2), the temperature of the solvothermal reaction is 90-120 ℃, and the reaction time is 24-54 hours.
7. Use of a tri-pyrazole ligand based metal-organic framework for the degradation of organic dyes according to any of claims 1 to 4, wherein the tri-pyrazole ligand based metal-organic framework is used for the photocatalytic degradation of methylene blue, congo red and methyl violet in organic dyes.
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