CN-116789941-B - Porphyrin-fluoroborofluorescence-based porous organic polymer, preparation method and photocatalysis application

Abstract

The invention discloses a porous organic polymer based on porphyrin-fluoroborofluorescence, a preparation method and photocatalysis application thereof, and belongs to the technical field of photocatalysis materials. According to the invention, the fluoro-boron fluorescent derivative is connected with porphyrin through alkynyl through a Sonogashira coupling reaction to prepare the porphyrin-fluoro-boron fluorescent porous organic polymer BPOP. Under illumination, the polymer adsorbs and photodegradation organic pollutants such as phenols, methyl orange and the like, so that the diphenyl sulfide is photo-catalytically oxidized into methyl phenyl sulfoxide with high selectivity and rapidness, and excellent photo-catalytic performance is shown.

Inventors

• GU PEIYANG
• WANG XIN
• ZENG BEIYAN
• WANG DANFENG

Assignees

• 常州大学

Dates

Publication Date

20260505

Application Date

20230721

Claims (4)

1. 1. The application of the porous organic polymer based on porphyrin-fluoroborofluorescence is characterized in that the porous organic polymer is used for photocatalytic degradation of organic pollutants, wherein the organic pollutants are bisphenol A; the porous organic polymer is prepared by a Sonogashira coupling reaction of a fluoboric fluorescence derivative and a porphyrin group-containing monomer; wherein the structure of the fluoboric fluorescence derivative is as follows: ; R1= Me,Et, , , , , , ; the porphyrin group-containing monomer structure is as follows: ; Wherein r2= , , , 。
2. 2. The use according to claim 1, wherein the molar ratio of the fluoroborofluorescence derivative to the porphyrin group-containing monomer is 2:1-5:1.
3. 3. The application of claim 1 or 2, wherein the fluoroborofluorescence derivative and the porphyrin group-containing monomer are subjected to reflux reaction by using tetrahydrofuran as a solvent under the conditions of a catalyst and an organic base to prepare the polymer, and the catalyst is cuprous iodide and tetra (triphenylphosphine) palladium.
4. 4. The method according to claim 3, wherein the organic base is triethylamine, diisopropylethylamine or diisopropylamine, and the volume ratio of the organic base to the solvent is 1:1-1:2.

Description

Porphyrin-fluoroborofluorescence-based porous organic polymer, preparation method and photocatalysis application Technical Field The invention belongs to the technical field of photocatalytic materials, and particularly relates to a preparation method and photocatalytic application of a porous organic polymer based on porphyrin-fluoroborofluorescence. Background The release of persistent organic pollutants into the environment is a global concern, and these chemicals are stable for long periods of time and accumulate in many animals and plants ultimately jeopardizing the life health and safety of humans. The traditional treatment method comprises biological adsorption degradation method, non-biological adsorption degradation method, compound direct degradation method, ultrasonic catalytic degradation method, photocatalytic degradation method and the like. However, these methods have the characteristics of incomplete removal, high cost, and the like. The photocatalytic technology has been developed as the most promising technology in the 20 th century because it can effectively degrade and completely mineralize persistent organic pollutants, and has advantages such as high efficiency with relatively low cost, eco-friendliness, and the like. The efficiency of the photocatalysis technology depends on the photocatalyst, and improving the adsorption performance and the catalytic degradation efficiency of the photocatalyst is still a technical bottleneck problem in the research field. Porous Organic Polymers (POPs) are widely used as recyclable heterogeneous catalysts in improving the adsorption and degradation properties of photocatalysts due to their controllable microporous structure and other advantages. The strong adsorptivity of the physical adsorption method and the thoroughly of degrading the organic pollutants by the photocatalytic oxidation method are sheared into one photocatalyst, and the development of a photocatalyst with high selective adsorption, high adsorption capacity and high photocatalytic activity is a key point in the research field. Porphyrin applications have been studied early in terms of degrading organic matter, and porphyrin-based POPs exhibit more efficient catalytic efficiency than traditional inorganic photocatalysts. A common method for improving the catalytic efficiency is to construct a D-a structure to promote the formation of an electric field built in the molecule, thereby improving the separation and transmission efficiency of photogenerated carriers. However, porphyrin has poor water solubility as a large pi structure with 18-electrons, resulting in limited adsorption capacity for contaminants, thereby limiting further improvement of catalytic efficiency. In addition, current research on photocatalysts is directed to the degradation of low concentration BPA (10-20 ppm), mainly due to the deactivation of high concentration BPA that is prone to cause catalyst pore plugging. Therefore, molecular design and material property improvement are required to be performed in consideration of practical application environments. Recently, methods for post-modification of POPs by introducing hydrophilic groups have been developed by Tao et al to increase hydrophilicity to enhance the efficiency of photodegradation of bisphenol A. The resulting polymer can achieve complete photodegradation of 50 ppm BPA solutions at 30 min. But this work has not yet addressed the degradation of BPA at higher concentrations, such as 100 ppm. In conclusion, the invention utilizes multiple molecular bond acting forces (hydrogen bond, pi-pi action and host-guest action) to improve the adsorption driving force to a certain extent, obtains adsorption-photodegradation balance, improves the overall photocatalytic degradation efficiency, and provides a D-pi-A double photosensitive center conjugated porous organic polymer for degrading BPA and dye (MO, MB, rhB) and a preparation method thereof. Disclosure of Invention The invention aims to provide a preparation method of a porphyrin-fluoroborofluorescence porous organic polymer and application thereof in photocatalytic degradation of organic pollutants and photocatalytic oxidation reaction, the porous organic polymer synthesized by the invention has the characteristics of large porosity, simple operation and adjustable structure, can adsorb and degrade organic pollutants, can high selectively and rapidly oxidize the phenyl sulfide into the methyl phenyl sulfoxide through photocatalysis, and has excellent photocatalytic performance. The invention is specifically realized by the following technical scheme that the fluorescent dye is prepared by a Sonogashira coupling reaction of a fluoboric derivative and a porphyrin unit. Wherein the structure of the fluoboric fluorescence derivative is as follows: ; R1= Me,Et,,,,,,; the porphyrin group-containing monomer is selected from the following structural formulas: Wherein r2= ,,,。 The invention provides a preparation method