1. A multidentate ligand porphyrin polymer and a preparation method thereof are characterized in that the structural formula is I or II:

wherein M is₁，M₂，M₃Is a metal ion.

2. A multidentate ligand porphyrin polymer according to claim 1, wherein the multidentate ligand porphyrin polymer is prepared by polymerizing two monomers, 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin or its metal derivatives, and 1, 10-phenanthroline-5, 6-dione or its metal derivatives.

3. A multidentate ligand porphyrin polymer according to claim 1 (II), wherein M is₁、M₂、M₃The metal ions can be the same metal ions or different metal ions.

4. A multidentate ligand porphyrin polymer according to claim 1, characterized in that it is prepared by a process comprising the steps of:

dissolving 5,10,15, 20-tetra (4-aminophenyl) porphyrin or a metal derivative thereof and 1, 10-phenanthroline-5, 6-diketone or a metal derivative thereof serving as raw materials in a molar ratio of 1: 2-2.05 in a mixed solvent of toluene/acetic acid water solution, and heating and reacting for 36-72 hours in a reaction kettle at 110-130 ℃;

pumping and filtering the mixed solution obtained in the step one, washing the obtained solid with ethanol, repeatedly washing with deionized water, and drying;

and thirdly, putting the solid obtained in the step II into a Soxhlet extractor, and carrying out Soxhlet extraction for 24-36 hours by taking tetrahydrofuran as a solvent.

And fourthly, washing and drying the solid purified in the third step to obtain the solid which is the multidentate ligand porphyrin polymer.

5. The multidentate ligand porphyrin polymer and the preparation method thereof as claimed in claim 1, wherein the step of (i) in claim 4 can be 5,10,15, 20-tetra (4-aminophenyl) porphyrin or the metal derivatives thereof and 1, 10-phenanthroline-5, 6-dione or the metal derivatives thereof as raw materials, the molar ratio is 1: 2-2.05, the raw materials are dissolved in a mixed solvent of o-dichlorobenzene, n-butanol and acetic acid, and the mixture is heated and reacted in a pressure-resistant bottle for 36-72 hours under the protection of nitrogen or argon.

Background

In recent years, with the rapid development of industry, a large amount of industrial wastewater is discharged into the natural environment, for example, a large amount of heavy metal wastewater generated in the production processes of mining, smelting, mechanical manufacturing, chemical engineering, electronic instruments and the like contains heavy metal ions such as mercury, chromium, cadmium, copper, nickel and the like, and wastewater discharged by printing and dyeing enterprises contains a large amount of highly toxic and carcinogenic aromatic organic pollutants and the like, and if the wastewater is not treated properly, the living environment and the body health of human beings are seriously threatened. At present, aromatic organic pollutants in wastewater can be removed by a photocatalytic degradation technology, and heavy metals in the wastewater cannot be decomposed and destroyed by various common water treatment methods, but only can transfer the existing positions and transform the physical and chemical states of the heavy metals. In real life, heavy metal/aromatic organic pollutants in industrial wastewater usually intersect and are discharged to form complex sewage, which adds great difficulty to the sewage treatment technology, generally needs multi-step treatment, is time-consuming and labor-consuming, and is difficult to adopt one-step process for complete treatment. Therefore, the method for treating the complex sewage containing the heavy metal/organic pollutant in one step is designed, and has important scientific research significance and industrial application value.

Disclosure of Invention

In order to obtain a photocatalyst for treating heavy metals and aromatic organic pollutants in industrial wastewater, a multidentate ligand porphyrin polymer and a preparation method thereof are invented.

The invention relates to a multidentate ligand porphyrin polymer, which is characterized in that the structural formula is I or II:

wherein M is a metal ion.

The invention relates to a multidentate ligand porphyrin polymer, which is characterized in that the preparation method comprises the following steps:

dissolving 5,10,15, 20-tetra (4-aminophenyl) porphyrin or a metal derivative thereof and 1, 10-phenanthroline-5, 6-diketone or a metal derivative thereof serving as raw materials in a molar ratio of 1: 2-2.05 in a mixed solvent of toluene/acetic acid water solution, and heating and reacting for 36-72 hours in a reaction kettle at 110-130 ℃;

pumping and filtering the mixed solution obtained in the step one, washing the obtained solid with ethanol, repeatedly washing with deionized water, and drying;

and thirdly, putting the solid obtained in the step II into a Soxhlet extractor, and carrying out Soxhlet extraction for 24-36 hours by taking tetrahydrofuran as a solvent.

And fourthly, washing and drying the solid purified in the third step to obtain the solid which is the multidentate ligand porphyrin polymer.

The invention relates to a multidentate ligand porphyrin polymer and a preparation method thereof, which are characterized in that the step of.

The invention has the technical effects that porphyrin is an important biomimetic catalyst, has stronger visible light and near infrared light absorption capability, a cross-linked porphyrin polymer formed by polymerizing 5,10,15, 20-tetra (4-aminophenyl) porphyrin and 1, 10-phenanthroline-5, 6-diketone, has the properties of porphyrin micromolecule and the special high molecular performance of the cross-linked polymer, can be used as a photocatalyst for oxidizing and degrading aromatic organic pollutants, simultaneously, as the center of the 5,10,15, 20-tetra (4-aminophenyl) porphyrin can coordinate heavy metal ions, the 1, 10-phenanthroline-5, 6-diketone can coordinate heavy metal ions, and after the polymerization reaction of the two monomers, N-containing coordination atoms can be coordinated with the heavy metal ions, therefore, the formed multidentate ligand can be used for treating heavy metal sewage, a porous structure formed after crosslinking can adsorb some toxic heavy metals, and some electrons generated in the photocatalysis process can also reduce some adsorbed high-valence toxic metals into non-toxic low-valence metals. In addition, the polymer has excellent thermal stability and chemical stability, is difficult to dissolve in water, conventional organic solvents and strong acid and alkali solutions, is not easy to cause secondary pollution, is easy to recycle and reuse, and reduces industrial cost, so that the multidentate ligand porphyrin polymer has wide application prospects in water treatment.

FIG. 1 is a chart of the IR spectrum of a multidentate porphyrin polymer prepared in example 1, which initially illustrates the covalent bonding of 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin and 1, 10-phenanthroline-5, 6-dione through chemical bonds. FIG. 2 shows a solid nuclear magnetic CP/MAS of a multidentate ligand porphyrin polymer prepared in example 1¹³C-NMR spectrum chart further showing that 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin and 1, 10-phenanthroline-5, 6-dione are polymerized to be covalently bonded through a chemical bond and form a crosslinked polymer.

Drawings

FIG. 1 is an infrared spectrum of a multidentate ligand porphyrin polymer.

FIG. 2 is a solid state nuclear magnetic carbon spectrum of a multidentate ligand porphyrin polymer.

Detailed description of the invention

The invention relates to a multidentate ligand porphyrin polymer, which is characterized in that the structural formula is I or II:

wherein M is a heavy metal ion.

The invention relates to a multidentate ligand porphyrin polymer, which is characterized in that the preparation method comprises the following steps:

dissolving 5,10,15, 20-tetra (4-aminophenyl) porphyrin or a metal derivative thereof and 1, 10-phenanthroline-5, 6-diketone or a metal derivative thereof serving as raw materials in a molar ratio of 1: 2-2.05 in a mixed solvent of toluene/acetic acid water solution, and heating and reacting for 36-72 hours in a reaction kettle at 110-130 ℃;

pumping and filtering the mixed solution obtained in the step one, washing the obtained solid with ethanol, repeatedly washing with deionized water, and drying;

and thirdly, putting the solid obtained in the step II into a Soxhlet extractor, and carrying out Soxhlet extraction for 24-36 hours by taking tetrahydrofuran as a solvent.

And fourthly, washing and drying the solid purified in the third step to obtain the solid which is the multidentate ligand porphyrin polymer.

The invention relates to a multidentate ligand porphyrin polymer and a preparation method thereof, which are characterized in that the first step can also be that 5,10,15, 20-tetra (4-aminophenyl) porphyrin or metal derivatives thereof and 1, 10-phenanthroline-5, 6-diketone or metal derivatives thereof are taken as raw materials, the molar ratio is 1: 2-2.05, the raw materials are dissolved in a mixed solvent of o-dichlorobenzene/n-butanol/acetic acid, and the mixture is heated and reacted for 36-72 hours in a pressure-resistant bottle under the protection of nitrogen or argon.

The process of the present invention is illustrated below.

Example 1

5,10,15, 20-tetrakis (4-aminophenyl) porphyrin (250mg, 0.37mmol) and 1, 10-phenanthroline-5, 6-dione (152.4mg, 0.74mmol) were dissolved in a mixed solvent of toluene (20 mL)/aqueous acetic acid (1mL, 3M), and the mixture was heated in a reaction vessel at 120 ℃ for 72 hours. Carrying out suction filtration on the obtained mixed solution, washing the obtained solid with ethanol, repeatedly washing with deionized water, and drying; and putting the dried solid into a Soxhlet extractor, carrying out Soxhlet extraction for 36h by using tetrahydrofuran as a solvent, washing the purified solid, and drying to obtain the solid, namely the polydentate ligand porphyrin polymer.

Example 2

Dissolving 5,10,15, 20-tetra (4-aminophenyl) porphyrin (250mg, 0.37mmol) and 1, 10-phenanthroline-5, 6-dione (152.4mg, 0.74mmol) in a mixed solvent of o-dichlorobenzene/n-butanol/acetic acid, and heating and reacting for 72 hours in a pressure bottle under the protection of nitrogen or argon; carrying out suction filtration on the obtained mixed solution, washing the obtained solid with ethanol, repeatedly washing with deionized water, and drying; and (4) putting the dried solid into a Soxhlet extractor, and carrying out Soxhlet extraction for 36h by using tetrahydrofuran as a solvent. And washing and drying the purified solid to obtain the solid, namely the multidentate ligand porphyrin polymer.

Example 3

Dissolving 5,10,15, 20-tetra (4-aminophenyl) porphyrin (250mg, 0.37mmol) and 1, 10-phenanthroline-5, 6-dione (152.4mg, 0.74mmol) in a mixed solvent of o-dichlorobenzene/n-butanol/acetic acid, and heating and reacting for 72 hours in a pressure bottle under the protection of nitrogen or argon; carrying out suction filtration on the obtained mixed solution, washing the obtained solid with ethanol, repeatedly washing with deionized water, and drying; and (4) putting the dried solid into a Soxhlet extractor, and carrying out Soxhlet extraction for 36h by using tetrahydrofuran as a solvent. Washing and drying the purified solid to obtain the multidentate ligand porphyrin polymer, dissolving the multidentate ligand porphyrin polymer in acetone solution, and adding excessive PdCl₂(262mg,1.48mmol), stirring for 12 hours at room temperature, filtering, washing and drying to obtain a solid which is the metal-containing multidentate ligand porphyrin polymer, wherein the PdCl is₂And may be replaced by chlorides or acetates of other metals.

Example 4

Dissolving 5,10,15, 20-tetra (4-aminophenyl) zinc porphyrin (273mg, 0.37mmol) and 1, 10-phenanthroline-5, 6-diketone cobalt chloride (252mg, 0.74mmol) with metal in a mixed solvent of o-dichlorobenzene, n-butanol and acetic acid, and heating and reacting for 72 hours in a pressure bottle under the protection of nitrogen or argon; carrying out suction filtration on the obtained mixed solution, washing the obtained solid with ethanol, repeatedly washing with deionized water, and drying; and (4) putting the dried solid into a Soxhlet extractor, and carrying out Soxhlet extraction for 36h by using tetrahydrofuran as a solvent. Washing the purified solid, drying, dissolving the multidentate ligand porphyrin polymer in acetone solution, adding NiCl₂(192mg,1.48mmol), stirring for 12 hours at room temperature, filtering, washing with water, and drying to obtain a solid, namely the multidentate ligand porphyrin polymer containing three different metals.