High-stability pollution gas purification antibacterial material

Abstract

The application discloses a high-stability pollution gas purification antibacterial material and relates to the field of multifunctional materials. The high-stability pollution gas purification antibacterial material is prepared by the following steps: first, preparing a conjugated microporous polymer through cross-coupling reaction of triphenylamine-4,4',4"-triboronic acid, 1,4-dibromonaphthalene and 1,2-dibromonaphthalene, and then generating nano zinc oxide on the surface of the conjugated microporous polymer by means of ultrasonic-assisted sol-gel method; the conjugated structure of the conjugated microporous polymer can make the electron more effectively delocalized in the molecule, thereby enhancing the overall stability of the material; under the cavitation effect of ultrasonic waves, the vibration of the molecule is intensified, and the nano zinc oxide can be better embedded into the microstructure on the surface of the polymer, thereby further enhancing the overall stability of the material; the conjugated microporous polymer is responsible for adsorbing pollution gas, and the nano zinc oxide is attached to the surface of the conjugated microporous polymer, thereby improving the ability of the conjugated microporous polymer to evolve pollution gas and resist bacteria; and the high-stability pollution gas purification antibacterial material prepared by the application has the effects of purifying pollution gas and resisting bacteria.

Description

Technical Field

[0001] This invention relates to the field of multifunctional materials technology, specifically to a highly stable polluted gas purification and antibacterial material. Background Technology

[0002] With the acceleration of industrialization and changes in modern lifestyles, pollutants such as volatile organic compounds (VOCs), sulfur dioxide (SO2), and nitrogen oxides (NOx) have become increasingly prevalent. x The continuous emission of pollutants such as nitrogen oxides and sulfur dioxide poses a threat to human health and the ecological environment. People are increasingly demanding higher quality of life and paying more attention to a healthy living environment. Whether in homes, workplaces, or public spaces, there is an urgent need for efficient and stable pollutant purification and antibacterial materials to ensure air quality and reduce microbial contamination.

[0003] For example, when choosing decoration materials and furniture, consumers are increasingly inclined to select products with environmentally friendly and antibacterial functions. In workplaces, good indoor air quality helps improve employee work efficiency and health, and reduces economic losses caused by sick leave. Therefore, developing a highly stable antibacterial material for purifying polluted gases that can meet public needs has significant social implications. Summary of the Invention

[0004] The purpose of this invention is to provide a highly stable antibacterial material for purifying polluted gases, in order to solve the problems existing in the prior art.

[0005] To solve the above-mentioned technical problems, the present invention provides the following technical solution: a highly stable pollutant gas purification and antibacterial material, wherein the highly stable pollutant gas purification and antibacterial material is prepared by loading nano-zinc oxide onto the surface of a self-made conjugated microporous polymer; The self-made conjugated microporous polymer was prepared by a cross-coupling reaction of triphenylamine-4,4',4"-triboronic acid and π-conjugated dibromonaphthalene monomer.

[0006] Furthermore, the nano-zinc oxide is generated on the surface of a conjugated microporous polymer via an ultrasound-assisted sol-gel method.

[0007] Furthermore, the π-conjugated dibromonaphthalene monomer is one of 1,4-dibromonaphthalene or 1,2-dibromonaphthalene.

[0008] Furthermore, a method for preparing a highly stable antibacterial material for purifying polluted gases includes the following preparation steps: (1) Under an argon atmosphere, triphenylamine-4,4',4"-triboronic acid and π-conjugated dibromonaphthalene were mixed at a molar ratio of 0.6~0.7:1 to obtain a reactant. Tetraphenylphosphine palladium with a molar ratio of 3~6% of the reactant was added, potassium carbonate with a mass of 6.0~6.2 times that of triphenylamine-4,4',4"-triboronic acid was added, and toluene aqueous solution with a mass of 47~50 times that of triphenylamine-4,4',4"-triboronic acid was added. Argon gas was continuously introduced at 10L / min for 40min. The mixture was stirred at 95~100℃ and 1200r / min for 3.5~4d. The precipitate was filtered, washed, purified, and then vacuum dried at -0.1MPa and 80℃ for 12h. After drying, the precipitate was ground to a particle size of 80~100nm to obtain the self-made conjugated microporous polymer. (2) Zinc acetate and monoethanolamine are mixed in a molar ratio of 1:1. A 0.5 mol / L zinc acetate solution is prepared using ethylene glycol ethyl ether as a solvent. The self-made conjugated microporous polymer and the zinc acetate solution are mixed in a volume ratio of 1:5~8. The mixture is soaked in ultrasonic waves for 5~10 min, filtered, dried in an oven at 150~160℃ for 30~60 min, and then annealed to obtain a highly stable antibacterial material for purifying polluted gases.

[0009] Furthermore, in step (1), the toluene aqueous solution is prepared by mixing toluene and water in a volume ratio of 3:1 and then ultrasonically sonicating for 15-30 minutes.

[0010] Furthermore, in step (1), the washing process involves washing with deionized water, methanol, and chloroform 2 to 3 times respectively.

[0011] Furthermore, in step (1), purification is performed using wood alcohol, acetone and chloroform as solvents, and each is purified by Soxhlet for 1 day.

[0012] Furthermore, the frequency of the ultrasonic wave in step (2) is 1.7 MHz.

[0013] Furthermore, in step (2), the annealing is performed at 180°C for 12 hours under a nitrogen atmosphere.

[0014] Compared with the prior art, the beneficial effects achieved by the present invention are: The highly stable antibacterial material for purifying polluted gases prepared by this invention effectively improves the material's stability and ability to purify polluted gases while achieving antibacterial effects.

[0015] First, a conjugated microporous polymer was prepared by cross-coupling reaction of triphenylamine-4,4',4"-triboronic acid, 1,4-dibromonaphthalene, and 1,2-dibromonaphthalene. Then, a highly stable pollutant gas purification and antibacterial material was obtained by generating nano-zinc oxide on the surface of the conjugated microporous polymer using an ultrasonic-assisted sol-gel method. The conjugated structure of the conjugated microporous polymer allows electrons to be more effectively delocalized within the molecule, thereby enhancing the overall stability of the material. Under the cavitation effect of ultrasound, the vibration of molecules is intensified, and the heat transfer accelerates the molecular motion on the polymer surface. Nano-zinc oxide can be better embedded into the microstructure of the polymer surface, forming a strong interaction with the polymer matrix, further enhancing the overall stability of the material. The conjugated microporous polymer is responsible for adsorbing pollutant gases. The nano-zinc oxide attached to the surface of the conjugated microporous polymer increases the effective adsorption area and improves the ability of the conjugated microporous polymer to purify pollutant gases and fight bacteria. Detailed Implementation

[0016] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0017] To more clearly illustrate the method provided by the present invention, the following embodiments are provided in detail. The test methods for various indicators of the highly stable polluted gas purification and antibacterial material prepared in the following embodiments are as follows: Thermal stability: The weight loss of stable pollutant gas purification antibacterial materials prepared by the same mass of the examples and comparative examples was tested by heating to 400°C at 10°C / min.

[0018] Antibacterial properties: The antibacterial materials for purifying polluted gases prepared by the same mass of the examples and comparative examples were tested for antibacterial properties in accordance with GB / T 21510-2008 "Test Method for Antibacterial Properties of Nano-Inorganic Materials".

[0019] Example 1 A method for preparing a highly stable antibacterial material for purifying polluted gases includes the following preparation steps: (1) Under an argon atmosphere, triphenylamine-4,4',4"-triboronic acid and 1,2-dibromonaphthalene were mixed at a molar ratio of 0.6:1 to obtain a reactant. 3% of tetratriphenylphosphine palladium was added to the reactant. Potassium carbonate was added at a mass ratio of 6.0 times that of triphenylamine-4,4',4"-triboronic acid. A toluene aqueous solution was added at a mass ratio of 47 times that of triphenylamine-4,4',4"-triboronic acid. The toluene aqueous solution was prepared by mixing toluene and water at a volume ratio of 3:1 and ultrasonically sonicating for 15 min. Argon gas was continued to be introduced at a rate of 10 L / min for 40 min. The mixture was stirred at 95 °C and 1200 r / min for 3.5 days. The precipitate was filtered and washed twice with deionized water, methanol and chloroform respectively. Soxhlet purification was performed for 1 day using wood alcohol, acetone and chloroform as solvents. The mixture was then vacuum dried at -0.1 MPa and 80 °C for 12 h. After drying, the mixture was ground to a particle size of 80 nm to obtain a self-made conjugated microporous polymer. (2) Zinc acetate and monoethanolamine were mixed in a molar ratio of 1:1. A 0.5 mol / L zinc acetate solution was prepared using ethylene glycol ethyl ether as a solvent. The self-made conjugated microporous polymer and the zinc acetate solution were mixed in a volume ratio of 1:5. The mixture was soaked in 1.7 MHz ultrasound for 5 min, filtered, dried in a 150 ℃ oven for 30 min, and then annealed at 180 ℃ for 12 h under a nitrogen atmosphere to obtain a highly stable pollutant gas purification antibacterial material.

[0020] Example 2 A method for preparing a highly stable antibacterial material for purifying polluted gases includes the following preparation steps: (1) Under an argon atmosphere, triphenylamine-4,4',4"-triboronic acid and 1,2-dibromonaphthalene were mixed at a molar ratio of 0.7:1 to obtain a reactant. 5% of tetratriphenylphosphine palladium was added to the reactant. 6.1 times the mass of potassium carbonate of triphenylamine-4,4',4"-triboronic acid was added. 48 times the mass of toluene aqueous solution of triphenylamine-4,4',4"-triboronic acid was added. The toluene aqueous solution was prepared by mixing toluene and water at a volume ratio of 3:1 and then sonicating for 20 min. Argon gas was continuously introduced at 10 L / min for 40 min. The mixture was stirred at 100 °C and 1200 r / min for 4 days. The precipitate was filtered and washed three times with deionized water, methanol, and chloroform, respectively. Then, Soxhlet purification was performed for 1 day using wood alcohol, acetone, and chloroform as solvents. The precipitate was dried under vacuum at -0.1 MPa and 80 °C for 12 h. After drying, the precipitate was ground to a particle size of 90 nm to obtain a self-made conjugated microporous polymer. (2) Zinc acetate and monoethanolamine were mixed in a molar ratio of 1:1. A 0.5 mol / L zinc acetate solution was prepared using ethylene glycol ethyl ether as a solvent. The self-made conjugated microporous polymer and the zinc acetate solution were mixed in a volume ratio of 1:7. The mixture was soaked in 1.7 MHz ultrasound for 8 min, filtered, dried in an oven at 155 ℃ for 45 min, and then annealed at 180 ℃ for 12 h under a nitrogen atmosphere to obtain a highly stable pollutant gas purification antibacterial material.

[0021] Example 3 A method for preparing a highly stable antibacterial material for purifying polluted gases includes the following preparation steps: (1) Under an argon atmosphere, triphenylamine-4,4',4"-triboronic acid and 1,2-dibromonaphthalene were mixed at a molar ratio of 0.7:1 to obtain a reactant. 6% of tetratriphenylphosphine palladium was added to the reactant. 6.2 times the mass of potassium carbonate of triphenylamine-4,4',4"-triboronic acid was added. 50 times the mass of toluene aqueous solution of triphenylamine-4,4',4"-triboronic acid was added. The toluene aqueous solution was prepared by mixing toluene and water at a volume ratio of 3:1 and then sonicating for 30 min. Argon gas was continuously introduced at 10 L / min for 40 min. The mixture was stirred at 100 °C and 1200 r / min for 4 days. The precipitate was filtered and washed three times with deionized water, methanol, and chloroform, respectively. Then, Soxhlet purification was performed for 1 day using wood alcohol, acetone, and chloroform as solvents. The precipitate was dried under vacuum at -0.1 MPa and 80 °C for 12 h. After drying, the precipitate was ground to a particle size of 100 nm to obtain a self-made conjugated microporous polymer. (2) Zinc acetate and monoethanolamine were mixed in a molar ratio of 1:1. A 0.5 mol / L zinc acetate solution was prepared using ethylene glycol ethyl ether as a solvent. The self-made conjugated microporous polymer and the zinc acetate solution were mixed in a volume ratio of 1:8. The mixture was soaked in 1.7 MHz ultrasound for 10 min, filtered, dried in a 160 ℃ oven for 60 min, and then annealed at 180 ℃ for 12 h under a nitrogen atmosphere to obtain a highly stable pollutant gas purification antibacterial material.

[0022] Comparative Example 1 Zinc acetate and monoethanolamine were mixed at a molar ratio of 1:1, and a 0.5 mol / L zinc acetate solution was prepared using ethylene glycol ethyl ether as a solvent. Bentonite particles with a particle size of 90 nm were mixed with the zinc acetate solution at a volume ratio of 1:7. The mixture was then soaked under 1.7 MHz ultrasound for 8 min, filtered, dried in an oven at 155 ℃ for 45 min, and then annealed at 180 ℃ for 12 h under a nitrogen atmosphere to obtain a highly stable antibacterial material for purifying polluted gases.

[0023] Comparative Example 2 (1) Under an argon atmosphere, triphenylamine-4,4',4"-triboronic acid and 1,2-dibromonaphthalene were mixed at a molar ratio of 0.7:1 to obtain a reactant. 5% of tetratriphenylphosphine palladium was added to the reactant. 6.1 times the mass of potassium carbonate of triphenylamine-4,4',4"-triboronic acid was added. 48 times the mass of toluene aqueous solution of triphenylamine-4,4',4"-triboronic acid was added. The toluene aqueous solution was prepared by mixing toluene and water at a volume ratio of 3:1 and then sonicating for 20 min. Argon gas was continuously introduced at 10 L / min for 40 min. The mixture was stirred at 100 °C and 1200 r / min for 4 days. The precipitate was filtered and washed three times with deionized water, methanol, and chloroform, respectively. Then, Soxhlet purification was performed for 1 day using wood alcohol, acetone, and chloroform as solvents. The precipitate was dried under vacuum at -0.1 MPa and 80 °C for 12 h. After drying, the precipitate was ground to a particle size of 90 nm to obtain a self-made conjugated microporous polymer. (2) Zinc acetate and monoethanolamine were mixed in a molar ratio of 1:1. A 0.5 mol / L zinc acetate solution was prepared using ethylene glycol ethyl ether as a solvent. The self-made conjugated microporous polymer and the zinc acetate solution were mixed in a volume ratio of 1:7. The mixture was soaked for 8 min, filtered, dried in an oven at 155℃ for 45 min, and then annealed at 180℃ for 12 h under a nitrogen atmosphere to obtain a highly stable pollutant gas purification antibacterial material.

[0024] Comparative Example 3 Under an argon atmosphere, triphenylamine-4,4',4"-triboronic acid and 1,2-dibromonaphthalene were mixed at a molar ratio of 0.7:1 to obtain a reactant. 5% of tetratriphenylphosphine palladium (at a molar ratio of the reactant) was added, along with 6.1 times the mass of potassium carbonate (triphenylamine-4,4',4"-triboronic acid) and 48 times the mass of toluene aqueous solution (toluene and water were mixed at a volume ratio of 3:1 and ultrasonicated for 20 min). Argon gas was then continuously introduced at a rate of 10 L / min for 40 min, and the mixture was stirred at 100 °C and 1200 r / min for 4 days. The precipitate was filtered and washed three times each with deionized water, methanol, and chloroform. Soxhlet purification was then performed for 1 day using wood alcohol, acetone, and chloroform as solvents. The precipitate was then vacuum dried at -0.1 MPa and 80 °C for 12 h. Finally, the precipitate was ground to a particle size of 90 nm to obtain a highly stable antibacterial material for purifying polluted gases.

[0025] Example of effect Table 1 below shows the performance analysis results of the highly stable pollutant gas purification and antibacterial materials of Examples 1 to 3 and Comparative Examples 1 to 3 of the present invention.

[0026] Table 1

[0027] A comparison of the experimental data from Example 2 and Comparative Example 1 reveals that the present invention prepares a conjugated microporous polymer using triphenylamine-4,4',4"-triboronic acid, 1,4-dibromonaphthalene, and 1,2-dibromonaphthalene via a cross-coupling reaction. The conjugated structure of the conjugated microporous polymer allows for more effective delocalization of electrons within the molecule, thereby enhancing the overall stability of the material. A comparison of the experimental data from Example 2 and Comparative Example 2 also reveals that the present invention uses an ultrasonic-assisted sol-gel method to generate nano-zinc oxide on the surface of the conjugated microporous polymer. Under the cavitation effect of ultrasound, molecular vibration is intensified, and the heat transfer accelerates molecular movement on the polymer surface. The nano-zinc oxide can be better embedded into the microstructure of the polymer surface, forming a strong interaction with the polymer matrix, further enhancing the overall stability of the material. A comparison of the experimental data from Example 2 and Comparative Example 3 further reveals that the conjugated microporous polymer of the present invention is responsible for adsorbing polluting gases. The nano-zinc oxide adheres to the surface of the conjugated microporous polymer, increasing the effective adsorption area and improving the conjugated microporous polymer's ability to purify polluting gases and its antibacterial properties.

[0028] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No markings in the claims should be construed as limiting the scope of the claims.

Claims

1. A highly stable antibacterial material for purifying polluted gases, characterized in that, The highly stable pollutant gas purification and antibacterial material is prepared by loading nano zinc oxide onto the surface of a self-made conjugated microporous polymer. The self-made conjugated microporous polymer was prepared by a cross-coupling reaction of triphenylamine-4,4',4"-triboronic acid and π-conjugated dibromonaphthalene monomer.

2. The highly stable polluted gas purification and antibacterial material according to claim 1, characterized in that, The nano-zinc oxide is generated on the surface of a conjugated microporous polymer using an ultrasound-assisted sol-gel method.

3. The highly stable polluted gas purification and antibacterial material according to claim 1, characterized in that, The π-conjugated dibromonaphthalene monomer is one of 1,4-dibromonaphthalene or 1,2-dibromonaphthalene.

4. A method for preparing a highly stable antibacterial material for purifying polluted gases, characterized in that, The preparation steps include the following: (1) Under an argon atmosphere, triphenylamine-4,4',4"-triboronic acid and π-conjugated dibromonaphthalene were mixed at a molar ratio of 0.6~0.7:1 to obtain a reactant. Tetraphenylphosphine palladium with a molar ratio of 3~6% of the reactant was added, potassium carbonate with a mass of 6.0~6.2 times that of triphenylamine-4,4',4"-triboronic acid was added, and toluene aqueous solution with a mass of 47~50 times that of triphenylamine-4,4',4"-triboronic acid was added. Argon gas was continuously introduced at 10L / min for 40min. The mixture was stirred at 95~100℃ and 1200r / min for 3.5~4d. The precipitate was filtered, washed, purified, and then vacuum dried at -0.1MPa and 80℃ for 12h. After drying, the precipitate was ground to a particle size of 80~100nm to obtain the self-made conjugated microporous polymer. (2) Zinc acetate and monoethanolamine are mixed in a molar ratio of 1:

1. A 0.5 mol / L zinc acetate solution is prepared using ethylene glycol ethyl ether as a solvent. The self-made conjugated microporous polymer and the zinc acetate solution are mixed in a volume ratio of 1:5~8. The mixture is soaked in ultrasonic waves for 5~10 min, filtered, dried in an oven at 150~160℃ for 30~60 min, and then annealed to obtain a highly stable antibacterial material for purifying polluted gases.

5. The method for preparing a highly stable antibacterial material for purifying polluted gases according to claim 4, characterized in that, The toluene aqueous solution in step (1) is prepared by mixing toluene and water in a volume ratio of 3:1 and then sonicating for 15 to 30 minutes.

6. The method for preparing a highly stable antibacterial material for purifying polluted gases according to claim 4, characterized in that, In step (1), the washing process involves washing with deionized water, methanol, and chloroform 2-3 times each.

7. The method for preparing a highly stable antibacterial material for purifying polluted gases according to claim 4, characterized in that, In step (1), purification was performed using wood alcohol, acetone and chloroform as solvents, and each was purified by Soxhlet for 1 day.

8. The method for preparing a highly stable antibacterial material for purifying polluted gases according to claim 4, characterized in that, The frequency of the ultrasonic wave in step (2) is 1.7 MHz.

9. The method for preparing a highly stable antibacterial material for purifying polluted gases according to claim 4, characterized in that, In step (2), the annealing is performed at 180°C for 12 hours under a nitrogen atmosphere.

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