Composite functional pollution gas purification functional material

Abstract

This invention discloses a composite functional material for purifying polluted gases and its preparation method, belonging to the field of purification materials technology. First, a UiO-66 magnetic metal-organic framework material is prepared by doping with iron oxide (Fe3O4), possessing a large specific surface area and abundant active sites, enabling rapid capture and absorption of pollutants. Simultaneously, the presence of Fe3O4 further adsorbs and degrades polluted gases, improving purification efficiency and reducing usage costs. Then, pyrithiol is grafted onto the material surface, forming reversible coordination bonds with zirconium ions. The presence of thiol groups preferentially adsorbs sulfides, reducing catalyst sulfur poisoning, protecting active sites, and dynamically repairing structural defects in the material. Finally, the hydroxyl groups on the surface of silver-doped nano-titanium dioxide particles synergistically react with the material to form a stable Ag-O-Ti complex, achieving a highly dispersed loading effect of the active components, enhancing photocatalytic activity, providing long-term release of silver ions, and simultaneously inactivating microorganisms contained in the polluted gas, thus enhancing the purification effect.

Description

Technical Field

[0001] This invention relates to the field of purification materials technology, specifically to a composite functional material for purifying polluted gases. Background Technology

[0002] With the acceleration of industrialization and the improvement of urbanization, air pollution has become increasingly severe, seriously threatening human health and the ecological environment. Composite functional materials for purifying pollutants, as an important means of controlling air pollution, have been widely used in industrial waste gas treatment and indoor air purification through the synergistic effects of multiple mechanisms such as physical adsorption and chemical catalysis. However, these materials still face many technical bottlenecks in practical applications, and their performance falls significantly short of the urgent needs of environmental protection. In industrial waste gas treatment scenarios, the pollution sources are complex, often containing multiple toxic and harmful gases such as sulfur dioxide, nitrogen oxides, and volatile organic compounds (VOCs). Traditional composite functional materials, due to limited adsorption sites, insufficient catalytic activity, or low mass transfer efficiency, struggle to achieve efficient simultaneous removal of multiple pollutants. For example, in the desulfurization and denitrification process of flue gas from coal-fired power plants, some composite catalysts have a conversion rate of less than 70% for nitrogen oxides, resulting in high concentrations of pollutants in the emitted gas, failing to meet increasingly stringent environmental standards. Furthermore, the material surface is easily covered or poisoned by pollutants, further reducing purification efficiency and requiring frequent equipment shutdowns for cleaning or material replacement, increasing operating costs.

[0003] Currently, most purification materials remove pollutants through physical adsorption or chemical fixation. However, these materials lack effective regeneration technologies after saturation or failure. For example, activated carbon-based composite materials typically require high-temperature desorption and regeneration after adsorbing VOCs. However, high-temperature treatment is not only energy-intensive but also prone to structural damage, resulting in a significant decrease in adsorption performance after regeneration. For composite functional materials containing precious metal catalysts, the recovery process is even more complex, requiring the separation of precious metals through chemical dissolution and extraction processes. This not only increases recovery costs but may also cause secondary pollution. Furthermore, in actual use, materials exposed to harsh environments such as high temperature, high humidity, and corrosive gases for extended periods are prone to physical structural collapse, deactivation of chemically active sites, or component loss, leading to gradual performance degradation. For instance, in automotive exhaust purification, the active sites of the composite catalyst in a three-way catalytic converter are gradually covered or sintered under the influence of high temperature and sulfur poisoning, resulting in a decrease in catalytic efficiency of approximately 10%-15% per year, with a service life typically not exceeding 50,000 kilometers. For photocatalytic composite materials used in indoor air purification, long-term exposure to light and humidity changes can lead to a reduction in active species such as hydroxyl radicals on the material surface, significantly reducing the purification effect over time. Short material lifespan not only increases replacement frequency and maintenance costs, but also exacerbates resource consumption and environmental pollution. Summary of the Invention

[0004] The purpose of this invention is to provide a composite functional material for purifying polluted gases and its preparation method, so as 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 composite functional material for purifying polluted gases, comprising the following preparation steps by weight: (1) Mix 12-16 parts zirconium chloride, 8-14 parts terephthalic acid, 2-4 parts glacial acetic acid, and 100-160 parts N,N-dimethylformamide evenly, add 1-3 parts iron oxide nanoparticles, ultrasonically disperse for 20-30 min, transfer to a reaction vessel, react at 120-180℃ for 12-30 h, cool naturally to room temperature after the reaction is completed, collect the solid, wash twice with deionized water and ethanol alternately, and dry in a 40℃ oven for 10-16 h to obtain magnetic UiO-66 material; (2) Disperse 10-16 parts of magnetic UiO-66 material in 60-140 parts of anhydrous ethanol, add 7-11 parts of 3-aminopropyltriethoxysilane, stir at 50-70℃ and 90rpm for 4-8h, filter to collect the solid, transfer and disperse to 50-80 parts of PBS buffer, add 3-5 parts of pyrithioneol under nitrogen protection, react at 45-55℃ and 110rpm for 10-14h, add 8-12 parts of silver-doped nano-titanium dioxide particles, continue stirring for 5-11h, collect the solid, wash 3 times with deionized water to obtain composite functional pollutant gas purification material.

[0006] Furthermore, the particle size of the iron oxide nanoparticles in step (1) is 10~50nm.

[0007] Furthermore, the frequency of the ultrasound in step (1) is 40 kHz.

[0008] Furthermore, the pH value of the PBS buffer in step (2) is 7.4.

[0009] Further, the preparation steps of silver-doped nano-titanium dioxide particles in step (2) are as follows: 5 parts tetrabutyl titanate and 50 parts anhydrous ethanol are mixed evenly, 1 part nitric acid solution is added dropwise at a rate of 1 drop / s, and stirred at 100 rpm for 2-3 hours. Then, 10 parts silver nitrate aqueous solution is added, mixed evenly, irradiated under ultraviolet light for 0.5-2 hours, placed in a calcination furnace, heated to 400℃, and calcined for 1-3 hours to obtain silver-doped nano-titanium dioxide particles.

[0010] Furthermore, the nitric acid content in the nitric acid solution is 65 wt%.

[0011] Furthermore, the concentration of the silver nitrate aqueous solution is 1 mol / L.

[0012] Furthermore, the ultraviolet light has a wavelength of 365 nm and a power of 100 mW / cm². 2 .

[0013] Furthermore, the heating rate of the calcining furnace is 2°C / min.

[0014] Furthermore, a composite functional pollutant gas purification material is prepared according to any of the above-described preparation methods.

[0015] Compared with the prior art, the beneficial effects achieved by the present invention are: This invention first prepares a UiO-66 magnetic metal-organic framework material by doping with iron oxide (Fe3O4), which has a large specific surface area and abundant active sites, enabling rapid capture and absorption of pollutants. Simultaneously, the presence of Fe3O4 further adsorbs and degrades polluting gases, improving purification efficiency. Furthermore, the magnetic material is easy to recycle, reducing usage costs. Next, pyrithiol is grafted onto the material surface, forming reversible coordination bonds with zirconium ions. The presence of thiol groups preferentially adsorbs sulfides, reducing catalyst sulfur poisoning, protecting active sites, and dynamically repairing structural defects in the material. Finally, the hydroxyl groups on the surface of silver-doped nano-titanium dioxide particles synergistically react with the material to form a stable Ag-O-Ti complex, achieving a highly dispersed loading effect of the active components, enhancing photocatalytic activity, and providing long-lasting release of silver ions. This simultaneously inactivates microorganisms contained in the polluting gases, avoiding single-stage purification and enhancing the overall purification effect. 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] Example 1 (1) Mix 12 parts zirconium chloride, 8 parts terephthalic acid, 2 parts glacial acetic acid and 100 parts N,N-dimethylformamide evenly, add 1 part iron oxide nanoparticles with a particle size of 10 nm, ultrasonically disperse at 40 kHz for 20 min, transfer to a reaction vessel, react at 120 ℃ for 12 h, cool naturally to room temperature after the reaction is completed, collect the solid, wash twice with deionized water and ethanol alternately, and dry in an oven at 40 ℃ for 10 h to obtain magnetic UiO-66 material; (2) Mix 5 parts tetrabutyl titanate and 50 parts anhydrous ethanol evenly, add 1 part 65wt% nitric acid solution dropwise at a rate of 1 drop / s, stir at 100 rpm for 2 hours, then add 10 parts 1mol / L silver nitrate aqueous solution, mix evenly, and stir at a wavelength of 365nm and a power of 100mW / cm. 2 The nano-titanium dioxide particles were irradiated under ultraviolet light for 0.5 h, placed in a calcination furnace, heated to 400 °C at a rate of 2 °C / min, and calcined for 1 h to obtain silver-doped nano-titanium dioxide particles. (3) Disperse 10 parts of magnetic UiO-66 material in 60 parts of anhydrous ethanol, add 7 parts of 3-aminopropyltriethoxysilane, stir at 50℃ and 90rpm for 4h, filter to collect solid, transfer and disperse to 50 parts of PBS buffer with pH value of 7.4, add 3 parts of pyrithiol under nitrogen protection, react at 45℃ and 110rpm for 10h, add 8 parts of silver-doped nano titanium dioxide particles, continue stirring for 5h, collect solid, wash 3 times with deionized water to obtain composite functional pollutant gas purification material.

[0018] Example 2 (1) Mix 14 parts zirconium chloride, 11 parts terephthalic acid, 3 parts glacial acetic acid and 130 parts N,N-dimethylformamide evenly, add 2 parts iron oxide nanoparticles with a particle size of 30 nm, ultrasonically disperse at 40 kHz for 25 min, transfer to a reaction vessel, react at 150 ℃ for 23 h, cool naturally to room temperature after the reaction is completed, collect the solid, wash twice with deionized water and ethanol alternately, and dry in an oven at 40 ℃ for 13 h to obtain magnetic UiO-66 material; (2) Mix 5 parts tetrabutyl titanate and 50 parts anhydrous ethanol evenly, add 1 part 65wt% nitric acid solution dropwise at a rate of 1 drop / s, stir at 100 rpm for 2.5 h, then add 10 parts 1mol / L silver nitrate aqueous solution, mix evenly, and stir at a wavelength of 365nm and a power of 100mW / cm. 2 The particles were irradiated with ultraviolet light for 1.5 hours, placed in a calcining furnace, heated to 400℃ at a rate of 2℃ / min, and calcined for 2 hours to obtain silver-doped nano-titanium dioxide particles. (3) 13 parts of magnetic UiO-66 material were dispersed in 100 parts of anhydrous ethanol, 9 parts of 3-aminopropyltriethoxysilane were added, and the mixture was stirred at 60℃ and 90 rpm for 6 h. The solid was filtered and transferred to 65 parts of PBS buffer with pH 7.4. Under nitrogen protection, 4 parts of pyrithione were added and the mixture was reacted at 50℃ and 110 rpm for 12 h. 10 parts of silver-doped nano-titanium dioxide particles were added and the mixture was stirred for another 8 h. The solid was collected and washed three times with deionized water to obtain a composite functional pollutant gas purification material.

[0019] Example 3 (1) Mix 16 parts zirconium chloride, 14 parts terephthalic acid, 4 parts glacial acetic acid, and 160 parts N,N-dimethylformamide evenly, add 3 parts iron oxide nanoparticles with a particle size of 50 nm, ultrasonically disperse at 40 kHz for 30 min, transfer to a reaction vessel, react at 180 ℃ for 30 h, cool naturally to room temperature after the reaction is completed, collect the solid, wash twice with deionized water and ethanol alternately, and dry in an oven at 40 ℃ for 16 h to obtain magnetic UiO-66 material; (2) Mix 5 parts tetrabutyl titanate and 50 parts anhydrous ethanol evenly, add 1 part 65wt% nitric acid solution dropwise at a rate of 1 drop / s, stir at 100 rpm for 3 hours, then add 10 parts 1mol / L silver nitrate aqueous solution, mix evenly, and stir at a wavelength of 365nm and a power of 100mW / cm. 2 The particles were irradiated with ultraviolet light for 2 hours, placed in a calcining furnace, heated to 400℃ at a rate of 2℃ / min, and calcined for 3 hours to obtain silver-doped nano-titanium dioxide particles. (3) Disperse 16 parts of magnetic UiO-66 material in 140 parts of anhydrous ethanol, add 11 parts of 3-aminopropyltriethoxysilane, stir at 70℃ and 90rpm for 8h, filter to collect the solid, transfer and disperse to 80 parts of PBS buffer with pH value of 7.4, add 5 parts of pyrithioneol under nitrogen protection, react at 55℃ and 110rpm for 14h, add 12 parts of silver-doped nano titanium dioxide particles, continue stirring for 11h, collect the solid, wash with deionized water 3 times to obtain composite functional pollutant gas purification material.

[0020] Comparative Example 1 The difference between Comparative Example 1 and Example 2 lies in step (1). Step (1) is changed to: mixing 14 parts zirconium chloride, 11 parts terephthalic acid, 3 parts glacial acetic acid, and 130 parts N,N-dimethylformamide evenly, reacting at 150°C for 23 hours, and then naturally cooling to room temperature after the reaction is completed. The solid is collected, washed twice with deionized water and ethanol alternately, and dried in a 40°C oven for 13 hours to obtain UiO-66 material; Step (3) is changed to: dividing 13 parts of UiO-66 material into Dispersed in 100 parts anhydrous ethanol, 9 parts 3-aminopropyltriethoxysilane were added, and the mixture was stirred at 60°C and 90 rpm for 6 hours. The solid was filtered and transferred to 65 parts PBS buffer with a pH of 7.4. Under nitrogen protection, 4 parts pyrithiol were added, and the mixture was reacted at 50°C and 110 rpm for 12 hours. Then, 10 parts silver-doped nano-titanium dioxide particles were added, and the mixture was stirred for another 8 hours. The solid was collected and washed three times with deionized water to obtain the composite functional pollutant gas purification material. The remaining steps were the same as in Example 2.

[0021] Comparative Example 2 The difference between Comparative Example 2 and Example 2 is that step (1) is omitted, and step (3) is changed to: dispersing 13 parts of iron(III) oxide in 100 parts of anhydrous ethanol, adding 9 parts of 3-aminopropyltriethoxysilane, stirring at 60°C and 90 rpm for 6 h, filtering to collect the solid, transferring and dispersing it in 65 parts of PBS buffer with a pH of 7.4, adding 4 parts of pyrithioneol under nitrogen protection, reacting at 50°C and 110 rpm for 12 h, adding 10 parts of silver-doped nano-titanium dioxide particles, continuing to stir for 8 h, collecting the solid, washing it 3 times with deionized water to obtain the composite functional pollutant gas purification material. The remaining steps are the same as in Example 2.

[0022] Comparative Example 3 The difference between Comparative Example 3 and Example 2 lies in step (3). Step (3) is changed to: dispersing 13 parts of magnetic UiO-66 material in 100 parts of anhydrous ethanol, adding 9 parts of 3-aminopropyltriethoxysilane, stirring at 60°C and 90 rpm for 6 hours, filtering to obtain the solid, transferring and dispersing it in 65 parts of PBS buffer with a pH of 7.4, adding 10 parts of silver-doped nano-titanium dioxide particles under nitrogen protection, continuing to stir for 8 hours, collecting the solid, washing it 3 times with deionized water, and obtaining the composite functional pollutant gas purification material. The remaining steps are the same as in Example 2.

[0023] Comparative Example 4 The difference between Comparative Example 4 and Example 2 lies in step (2). Step (2) is changed to: 5 parts tetrabutyl titanate and 50 parts anhydrous ethanol are mixed evenly, 1 part 65wt% nitric acid solution is added dropwise at a rate of 1 drop / s, stirred at 100 rpm for 2.5 h, placed in a calcination furnace, heated to 400℃ at a rate of 2℃ / min, and calcined for 2 h to obtain nano-titanium dioxide particles; Step (3) is changed to: 13 parts magnetic UiO-66 material are dispersed in 100 parts anhydrous ethanol, 9 parts 3-aminopropyltriethoxysilane are added, stirred at 60℃ and 90 rpm for 6 h, filtered to obtain solid, transferred and dispersed in 65 parts PBS buffer with a pH of 7.4, 4 parts pyrithiol are added under nitrogen protection, reacted at 50℃ and 110 rpm for 12 h, 10 parts nano-titanium dioxide particles are added, stirred for another 8 h, the solid is collected, washed 3 times with deionized water, and a composite functional pollutant gas purification material is obtained. The remaining steps are the same as in Example 2.

[0024] Comparative Example 5 The difference between Comparative Example 5 and Example 2 is that step (2) is omitted, and step (3) is changed as follows: 13 parts of magnetic UiO-66 material are dispersed in 100 parts of anhydrous ethanol, 9 parts of 3-aminopropyltriethoxysilane are added, and the mixture is stirred at 60°C and 90 rpm for 6 h. The solid is filtered and transferred to 65 parts of PBS buffer with a pH of 7.4. Under nitrogen protection, 4 parts of pyrithioneol are added, and the mixture is reacted at 50°C and 110 rpm for 12 h. 10 parts of silver nanoparticles with a particle size of 20 nm are added, and the mixture is stirred for another 8 h. The solid is collected and washed three times with deionized water to obtain the composite functional pollutant gas purification material. The remaining steps are the same as in Example 2.

[0025] Example of effect Table 1 below shows the performance analysis results of the composite functional pollutant gas purification materials of Examples 1 to 3 and Comparative Examples 1 to 5 of the present invention.

[0026] Table 1

[0027] A comparison of the experimental data from Examples 1, 2, and 3 with Comparative Examples 1 and 2 reveals that the UiO-66 magnetic metal-organic framework material prepared by doping with iron oxide (Fe3O4) possesses a large specific surface area and abundant active sites, enabling rapid capture and absorption of pollutants. Furthermore, the presence of iron oxide further adsorbs and degrades polluting gases, improving purification efficiency. Additionally, the magnetic material is easy to recycle, reducing usage costs. A comparison of the experimental data from Examples 1, 2, and 3 with Comparative Example 3 shows that grafting pyrithiol onto the material surface forms reversible coordination bonds with zirconium ions. The presence of thiol groups preferentially adsorbs sulfides, reducing catalyst sulfur poisoning, protecting active sites, dynamically repairing structural defects, and extending the material's lifespan. A comparison of the experimental data from Examples 1, 2, and 3 with Comparative Examples 4 and 5 shows that utilizing the synergistic reaction between the hydroxyl groups on the surface of silver-doped nano-titanium dioxide particles and the material forms a stable Ag-O-Ti complex, achieving a highly dispersed loading effect of the active components, enhancing photocatalytic activity, providing long-term release of silver ions, and simultaneously inactivating microorganisms contained in polluting gases, avoiding single-stage purification and enhancing the purification effect.

[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 composite functional material for purifying polluted gases, characterized in that, By weight, the preparation steps include the following: (1) Mix 12-16 parts zirconium chloride, 8-14 parts terephthalic acid, 2-4 parts glacial acetic acid, and 100-160 parts N,N-dimethylformamide evenly, add 1-3 parts iron oxide nanoparticles, ultrasonically disperse for 20-30 min, transfer to a reaction vessel, react at 120-180℃ for 12-30 h, cool naturally to room temperature after the reaction is completed, collect the solid, wash twice with deionized water and ethanol alternately, and dry in a 40℃ oven for 10-16 h to obtain magnetic UiO-66 material; (2) Disperse 10-16 parts of magnetic UiO-66 material in 60-140 parts of anhydrous ethanol, add 7-11 parts of 3-aminopropyltriethoxysilane, stir at 50-70℃ and 90rpm for 4-8h, filter to collect the solid, transfer and disperse to 50-80 parts of PBS buffer, add 3-5 parts of pyrithioneol under nitrogen protection, react at 45-55℃ and 110rpm for 10-14h, add 8-12 parts of silver-doped nano-titanium dioxide particles, continue stirring for 5-11h, collect the solid, wash 3 times with deionized water to obtain composite functional pollutant gas purification material.

2. The composite functional pollutant gas purification material according to claim 1, characterized in that, The particle size of the iron oxide nanoparticles in step (1) is 10~50nm.

3. The composite functional pollutant gas purification material according to claim 1, characterized in that, The frequency of the ultrasound in step (1) is 40 kHz.

4. The composite functional pollutant gas purification material according to claim 1, characterized in that, The pH value of the PBS buffer in step (2) is 7.

4.

5. The composite functional pollutant gas purification material according to claim 1, characterized in that, The preparation steps of silver-doped nano-titanium dioxide particles in step (2) are as follows: 5 parts tetrabutyl titanate and 50 parts anhydrous ethanol are mixed evenly, 1 part nitric acid solution is added dropwise at a rate of 1 drop / s, and stirred at 100 rpm for 2-3 hours. Then, 10 parts silver nitrate aqueous solution is added, mixed evenly, irradiated under ultraviolet light for 0.5-2 hours, placed in a calcination furnace, heated to 400℃, and calcined for 1-3 hours to obtain silver-doped nano-titanium dioxide particles.

6. The composite functional pollutant gas purification material according to claim 5, characterized in that, The nitric acid content in the nitric acid solution is 65 wt%.

7. The composite functional pollutant gas purification material according to claim 5, characterized in that, The concentration of the silver nitrate aqueous solution is 1 mol / L.

8. The composite functional pollutant gas purification material according to claim 5, characterized in that, The ultraviolet light has a wavelength of 365nm and a power of 100mW / cm². 2 .

9. The composite functional pollutant gas purification material according to claim 1, characterized in that, The heating rate of the calcining furnace is 2℃ / min.

10. A composite functional material for purifying polluted gases, characterized in that, Prepared according to any one of the preparation methods described in claims 1-9.

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