CN-121466995-B - Magnetic phosphorus-oxygen-based super-crosslinked porous material, and preparation method and application thereof

Abstract

The invention relates to the technical field of radioactive wastewater treatment materials, in particular to a magnetic phosphorus-oxygen-based super-crosslinked porous material, a preparation method and application thereof. The invention provides a preparation method of a magnetic phosphorus-oxygen-based super-crosslinked porous material, which is characterized in that a precursor polydopamine coated magnetic nano particle is used as a matrix, p-dichlorobenzene is used as a crosslinking agent, phenylphosphonic acid is used as a phosphorus-oxygen functional monomer, and the magnetic phosphorus-oxygen-based super-crosslinked porous material is prepared through Friedel-Crafts alkylation reaction catalyzed by a catalyst. The magnetic phosphorus-oxygen-based super-crosslinked porous material has the advantages of high U (VI) adsorption capacity, excellent selectivity and magnetic separation characteristics, can efficiently treat uranium-containing wastewater, and solves the problems of difficult separation, low adsorption capacity and insufficient selectivity of the traditional adsorption material.

Inventors

• HE YAN
• PING SONG
• WEN SHUNA
• DU QINGWANG
• LI CUIZHEN
• ZHANG QINGHUA
• JIN TIANXIANG
• YU FENGTAO
• YUAN DINGZHONG

Assignees

• 东华理工大学

Dates

Publication Date

20260508

Application Date

20251119

Claims (10)

1. 1. The preparation method of the magnetic phosphorus-oxygen-based super-crosslinked porous material is characterized by comprising the following steps of: The mixed solution of dopamine and ferroferric oxide is subjected to self-aggregation reaction, and a polydopamine coating layer is formed on the surface of the ferroferric oxide, so that polydopamine coated magnetic nano particles are obtained; Under inert atmosphere, poly-dopamine coated magnetic nano particles are used as a matrix, p-dichlorobenzene is used as a cross-linking agent, phenylphosphonic acid is used as a phosphorus-oxygen functional monomer in a solvent, and Friedel-Crafts alkylation reaction is carried out under the action of a catalyst, so that the magnetic phosphorus-oxygen super-crosslinked porous material is obtained.
2. 2. The preparation method of the magnetic phosphorus oxide-based super-crosslinked porous material according to claim 1, wherein the mass ratio of dopamine to ferroferric oxide is 1-1.2:1; the mixed solution of the dopamine and the ferroferric oxide is obtained by dissolving the dopamine in a Tris-hydrochloric acid buffer solution and uniformly dispersing the dopamine and the ferroferric oxide, wherein the concentration of the Tris-hydrochloric acid buffer solution is 18 mmol/L-20 mmol/L.
3. 3. The preparation method of the magnetic phosphorus oxide-based super-crosslinked porous material according to claim 1, wherein the mass ratio of polydopamine coated magnetic nanoparticles to dichlorobenzene is 1:1.3-1.4; The molar ratio of the p-dichlorobenzyl to the phenylphosphonic acid is 1:1-3; The mass ratio of the catalyst to the p-dichlorobenzene is 1:1-1.2.
4. 4. The method for preparing the magnetic phosphorus oxide-based super-crosslinked porous material according to claim 1, wherein the catalyst is ferric trichloride, aluminum trichloride or zinc chloride, and the solvent is 1, 2-dichloroethane or dibromomethane.
5. 5. The preparation method of the magnetic phosphorus-oxygen-based super-crosslinked porous material according to claim 1, wherein the reaction temperature of Friedel-Crafts alkylation reaction is 60-80 ℃, the reaction time is 20-24 h, and the inert atmosphere is nitrogen atmosphere.
6. 6. A magnetic phosphorus oxide-based super-crosslinked porous material, which is characterized by being prepared by the preparation method of the magnetic phosphorus oxide-based super-crosslinked porous material according to any one of claims 1-5.
7. 7. Use of a magnetic phosphorus oxide-based super-crosslinked porous material according to claim 6 as an adsorbent in uranium-containing wastewater treatment.
8. 8. The application of the magnetic phosphorus oxide-based super-crosslinked porous material as an adsorbent in uranium-containing wastewater treatment according to claim 7, wherein the specific application method is that the magnetic phosphorus oxide-based super-crosslinked porous material is added into the uranium-containing wastewater, and after the adsorption treatment, solid-liquid separation is realized through an external magnetic field.
9. 9. The application of the magnetic phosphorus oxide-based super-crosslinked porous material as an adsorbent in uranium-containing wastewater treatment, according to claim 8, wherein the initial concentration of U (VI) in the uranium-containing wastewater is 20-250 mg/L, the pH of the uranium-containing wastewater is 5.5-6, and the solid-liquid ratio of the uranium-containing wastewater to the magnetic phosphorus oxide-based super-crosslinked porous material is 0.2-0.3 g/L.
10. 10. The use of the magnetic phosphorus oxide based super-crosslinked porous material as an adsorbent in uranium-containing wastewater treatment according to claim 8, wherein the regeneration method of the magnetic phosphorus oxide based super-crosslinked porous material is as follows: taking a nitric acid solution with the concentration of 1.5 mol/L-2 mol/L as a regeneration solution; soaking the used magnetic phosphorus oxide super-crosslinked porous material in a nitric acid solution for desorption regeneration, washing with water, and drying to obtain a regenerated magnetic phosphorus oxide super-crosslinked porous material; The magnetic phosphorus-oxygen-based super-crosslinked porous material after use is used for adsorbing uranium-containing wastewater.

Description

Magnetic phosphorus-oxygen-based super-crosslinked porous material, and preparation method and application thereof Technical Field The invention relates to the technical field of radioactive wastewater treatment materials, in particular to a magnetic phosphorus-oxygen-based super-crosslinked porous material, a preparation method and application thereof. Background Nuclear energy is taken as a low-carbon and high-efficiency clean energy and plays a key role in energy transformation, but development of the nuclear energy is accompanied with a large amount of uranium-containing wastewater generated in the uranium resource development and utilization process. If uranium-containing wastewater is not properly treated, uranium (U (VI)) is accumulated in the environment for a long time as a radioactive element, and the ecological system and human health are endangered through soil, water sources and food chains, so that efficient treatment of the uranium-containing wastewater becomes an important guarantee for sustainable development of nuclear energy. The adsorption method is one of the mainstream technologies of uranium-containing wastewater treatment at present because of the advantages of simple operation, low cost, wide applicability and the like, and the core of the adsorption method is the research and development of high-performance adsorption materials. The porous organic polymer is POPs for short, and has great potential in the adsorption field by virtue of the characteristics of high specific surface area, abundant pore structures, functional modification and the like. However, the conventional POPs have the problems of difficult solid-liquid separation and complicated recovery operation, and limit practical application. Researchers try to use magnetic materials as adsorbents and realize rapid separation through an external magnetic field, but the single magnetic matrix has insufficient surface functional groups and insufficient adsorption capacity and selectivity to U (VI). Disclosure of Invention The invention provides a magnetic phosphorus-oxygen-based super-crosslinked porous material, a preparation method and application thereof, and aims to solve the problems of difficult separation, low adsorption capacity and insufficient selectivity of the traditional adsorption material. According to the invention, a functional group strategy is introduced through a one-step method, the magnetic separation characteristic is combined with the high affinity of the phosphorus-oxygen functional group, so that the magnetic phosphorus-oxygen super-crosslinked porous material is prepared, the efficient adsorption and convenient recovery of U (VI) in uranium-containing wastewater are realized, and a novel high-performance material is provided for radioactive wastewater treatment. The magnetic phosphorus-oxygen-based super-crosslinked porous material has the advantages of high U (VI) adsorption capacity, excellent selectivity and magnetic separation characteristics, can efficiently treat uranium-containing wastewater, and solves the problems of difficult separation, low adsorption capacity and insufficient selectivity of the traditional adsorption material. In order to achieve the above object, the technical scheme of the present invention is as follows. The invention provides a preparation method of a magnetic phosphorus oxide-based super-crosslinked porous material, which comprises the following steps: The method comprises the steps of carrying out self-aggregation reaction on a mixed solution of dopamine and ferroferric oxide, forming a polydopamine coating layer on the surface of the ferroferric oxide to obtain polydopamine coated magnetic nano particles, carrying out Friedel-Crafts alkylation reaction on polydopamine coated magnetic nano particles serving as a matrix and p-dichlorobenzene serving as a crosslinking agent and phenylphosphonic acid serving as a phosphorus-oxygen functional monomer in a solvent under the action of a catalyst in an inert atmosphere to obtain the magnetic phosphorus-oxygen-based super-crosslinked porous material. Preferably, the mass ratio of the dopamine to the ferroferric oxide is 1-1.2:1, the mixed solution of the dopamine and the ferroferric oxide is obtained by dissolving the dopamine in a Tris-hydrochloric acid buffer solution and uniformly dispersing the dopamine and the ferroferric oxide, and the concentration of the Tris-hydrochloric acid buffer solution is 18-20 mmol/L. Preferably, in the preparation process of the polydopamine coated magnetic nano particles, the reaction system is stirred for 12 hours at room temperature, and the product is alternately washed for more than 3 times by deionized water and ethanol and dried for 10 hours at 60 ℃. Preferably, the mass ratio of the polydopamine coated magnetic nano particles to the p-dichlorobenzene is 1:1.3-1.4, the molar ratio of the p-dichlorobenzene to the phenylphosphonic acid is 1:1-3, and the mass ratio of the catalyst to the