CN115467047B - Preparation method of highly efficient antibacterial photocatalytic continuous alumina fiber - Google Patents

Abstract

The invention relates to the technical field of inorganic oxide fibers, in particular to a preparation method of an efficient antibacterial photocatalytic continuous alumina fiber, wherein the alumina continuous fiber is prepared by taking aluminum salt as an aluminum source, doping a certain amount of zinc salt and adopting a sol-gel method; the high-efficiency antibacterial photocatalysis function is contributed by the zinc oxide nano rod array on the surface of the continuous alumina fiber, in the process of preparing the alumina continuous fiber by doping zinc salt sol-gel method, a shaped nuclear point is constructed on the surface of the continuous alumina fiber, and then the continuous alumina fiber with the zinc oxide nano rod array on the surface is prepared after the surface grows by a hydrothermal method. The preparation process is continuous, the composite of the aluminum oxide and the zinc oxide enables the material to have a core-shell structure, the surface of the zinc oxide nano rod needle array is as a shell layer, and the composite structure can convert oxygen and water into oxygen free radical and hydrogen peroxide, enhance the antibacterial effect of the surface zinc oxide and has excellent performance in the aspects of water pollution purification and the like.

Description

Preparation method of highly efficient antibacterial photocatalytic continuous alumina fiber

Technical field

The present invention relates to the technical field of inorganic oxide fibers, and in particular, to a preparation method of a highly efficient antibacterial photocatalytic continuous alumina fiber.

Background technique

The extensive development and utilization of fossil resources has caused many environmental pollution problems, which have had many adverse effects on human development and social progress. Improving pollution and obtaining pure, pollution-free air and water resources are an arduous but long-term task we are currently facing. There are many ways to solve environmental problems, such as physical adsorption, chemical precipitation, catalysis, etc. However, traditional filter materials have short service life, no antibacterial function, low filtration efficiency, and cannot be recycled. Therefore, it is of great significance to develop efficient, green and recyclable new filter materials with photocatalytic synergistic antibacterial properties.

Contents of the invention

The purpose of the present invention is to solve the shortcomings in the existing technology and propose a method for preparing high-efficiency antibacterial photocatalytic continuous alumina fibers, which can be used in air and water pollution treatment to solve the problem of short service life of traditional filter materials. Problems such as inability to be recycled and low catalytic efficiency.

In order to achieve the above objects, the present invention adopts the following technical solutions:

A method for preparing high-efficiency antibacterial photocatalytic continuous alumina fibers, which consists of continuous alumina fibers and surface-grown zinc oxide nanorod arrays. The specific steps are as follows:

S1. Preparation method of continuous alumina fiber

Using aluminum salt and metal aluminum alkoxide as the aluminum source, the material ratio of the aluminum source to water is 1:10-1:30, and the material ratio of the aluminum salt to the metal aluminum alkoxide is 1:0.5-1:3; Dissolve the aluminum salt in water, add AIP under reflux and stirring conditions at 60℃-80℃, react for about 8-24 hours, AIP will be completely hydrolyzed, use filter paper to filter impurities, and obtain a clear and transparent sol;

Weigh a certain mass of zinc salt and add it to water, stir at 60°C-80°C until uniformly dispersed; finally, slowly add the zinc salt-containing sol solution to the aluminum salt-containing sol, and continue stirring until a uniformly mixed sol is formed;

Mix the above mixed sol and a certain amount of catalyst in different proportions at room temperature, stir to mix evenly, and then place it in a 60°C-80°C water bath to age to a suitable viscosity to obtain a transparent spinnable sol, which is then spun to obtain surface loading. Continuous α-A1 ₂ O ₃ fiber with zinc oxide crystal nucleation points;

S2. Growth method of zinc oxide nanorods on the surface of continuous alumina fibers

Mix ammonium salt, zinc salt and deionized water in a certain proportion, and stir continuously for 12-24 hours at room temperature to prepare the required rod-shaped nano-zinc oxide array growth solution;

Send the alumina continuous fiber into the reaction device, keep it at 65-100℃ for 6-10h, cool to room temperature and let it stand for 10h. After the rod-shaped nano-zinc oxide array on the surface has completely grown, pass the alumina continuous fiber through the water tank. Wash repeatedly several times to remove excess solvent and other impurities. Finally, put the alumina fiber into the oven and dry it at 45-75°C for 20-60 minutes to obtain efficient antibacterial light with zinc oxide nanorod arrays grown on the surface. Catalyzed continuous alumina fibers.

Preferably, in step S1, the aluminum salt is one or any combination of aluminum chloride, aluminum nitrate, aluminum acetate or aluminum isopropoxide; the zinc salt is zinc chloride, zinc carbonate, zinc acetate, zinc acetate Or one or any combination of zinc nitrates; the ammonium salts are hexamethylphosphophthaletriamine, hexamethylenediamine, ethylenediamine, cetyltrimethylammonium bromide, tetramethylammonium bromide, One or a mixture of cetyltrimethylammonium chloride and tetradecyltrimethylammonium bromide.

Preferably, in step S1, the doping ratio of zinc salt is 2 to 10 wt%.

Preferably, the fiber diameter of the continuous α-A1 ₂ O ₃ fiber prepared in step S1 is 1 to 10 μm, the fiber phase composition is α-Al ₂ O ₃ , γ-Al ₂ O ₃ , and the fiber element composition is Al, O , Zn.

Preferably, in step S2, zinc oxide crystal nuclei are evenly distributed on the surface of the continuous alumina fiber, the diameter of the zinc oxide crystal nucleus is 5 to 250 nm, and the distribution ratio of zinc oxide crystal nuclei on the surface of the continuous alumina fiber is 30 to 80 pieces/ μm ² .

By adopting the above technical solution: the alumina continuous fiber is prepared by using aluminum salt as the aluminum source, doping a certain amount of zinc salt, and using the sol-gel method. The highly efficient antibacterial photocatalytic function is contributed by the zinc oxide nanorod array on the surface of the continuous alumina fiber. In the process of preparing the alumina continuous fiber by doping zinc salt sol-gel method, nucleation points are constructed on the surface of the continuous alumina fiber, and then through Continuous alumina fibers with zinc oxide nanorod arrays on the surface were grown by hydrothermal method. The advantages of this design are: the preparation process is continuous, nano-zinc oxide exists in the form of nano-rods in the structure, and has strong durability; and the composite of aluminum oxide/zinc oxide gives the material a core-shell structure, and the zinc oxide nano-rod needle array is like Shell layer, this composite structure can convert oxygen and water into oxygen free radicals and hydrogen peroxide, enhance the antibacterial effect of surface zinc oxide, and also has excellent performance in water pollution purification, etc. At the same time, due to the continuous alumina fiber itself With high temperature resistance, after gas or liquid filtration, surface pollutants can be removed through high temperature treatment to achieve the purpose of green regeneration and recycling.

Preferably, in step S2, the diameter of the zinc oxide nanorods is 100-500 nm, and the length of the zinc oxide nanorods is 300-1500 nm.

By adopting the above technical solution: Here, the zinc oxide nanorod array is prepared by a simple one-step hydrothermal method. The growth of the rod-shaped zinc oxide array on the surface of the continuous alumina fiber makes the alumina filament resistant to Gram-positive and Gram-negative bacteria. and fungi have excellent antibacterial effects, and the core-shell structure composed of aluminum oxide/zinc oxide composite can convert oxygen and water into oxygen free radicals and hydrogen peroxide, enhance the antibacterial effect of surface zinc oxide, and play a role in photocatalytic purification of water pollution and It has excellent performance in environmental antibacterial aspects.

Compared with the prior art, the present invention has the following beneficial effects:

1. The preparation process of the present invention is continuous and convenient for large-scale production; among them, nano-zinc oxide exists in the structure in the form of nano-rods and has strong durability; and the composite of aluminum oxide/zinc oxide makes the material have a core-shell structure, and the zinc oxide nano-rod needles The array acts like a shell on the surface. This composite structure can convert oxygen and water into oxygen free radicals and hydrogen peroxide, enhance the antibacterial effect of surface zinc oxide, and also has excellent performance in water pollution purification and other aspects.

2. Due to the high temperature resistance of the continuous alumina fiber itself in the present invention, after gas or liquid filtration, surface pollutants can be removed through high temperature treatment to achieve the purpose of green regeneration and recycling.

Description of the drawings

Figure 1 is an axial view of the alumina continuous fiber in the present invention;

Figure 2 is a meridional diagram of alumina continuous fibers in the present invention;

Figure 3 is an axial view of the alumina continuous fiber grown by the hydrothermal method in the present invention;

Figure 4 is a fiber meridional diagram of the alumina continuous fiber grown by the hydrothermal method in the present invention.

In the picture: 1 aluminum oxide continuous fiber, 2 zinc oxide crystal nucleation points, 3 zinc oxide nanorods.

Detailed ways

The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the accompanying drawings, so that those skilled in the art can better understand the advantages and features of the present invention, and thereby make the protection scope of the present invention clearer. definition. The embodiments described in the present invention are only some of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other implementations obtained by those of ordinary skill in the art without creative work are Examples, all belong to the protection scope of the present invention.

Example 1:

A method for preparing high-efficiency antibacterial photocatalytic continuous alumina fibers, which consists of continuous alumina fibers and an array of zinc oxide nanorods 3 grown on the surface. The specific steps are as follows:

S1. Preparation method of continuous alumina fiber

Aluminum salts and aluminum isopropoxide (AIP) are used as aluminum sources, where the aluminum salts are A1C1 ₃ ·6H ₂ O and Al(NO ₃ ) ₃ ·9H ₂ O respectively. The material ratio of the aluminum source to water is 1: 30. The material ratio of aluminum salt to AIP is 1:3. Dissolve the aluminum salt in water, add AIP under reflux and stirring conditions at 80°C, react for about 24 hours, AIP is completely hydrolyzed, and use filter paper to filter impurities to obtain a relatively clear and transparent sol.

Weigh a certain mass of zinc chloride (ZnC1 ₂ ·6H ₂ O) and add it to water, stir at 80°C until evenly dispersed; finally, slowly add the aqueous solution containing zinc chloride to the sol containing aluminum salt, and continue stirring until A uniformly mixed sol is formed.

Dissolve copper chloride (CuCl ₂ ·2H ₂ O) as a catalyst in a mixed solution of formic acid (HCOOH), glacial acetic acid (CH ₃ COOH) and water, add aluminum powder, and react under reflux and stirring conditions at 100°C for 4.5 hours. Use filter paper to filter out the displaced copper to obtain a transparent and excessively acidic basic aluminum methylacetate solution. The ratio of the amounts of each raw material is Al:HCOOH:CH ₃ COOH:H ₂ O=1:4.5:3:24, and Al:CuC1 ₂ ·2H ₂ O=1:0.011.

Mix the above sol and basic aluminum methylacetate solution in different proportions at room temperature, stir to mix evenly, and then place it in an 80°C water bath for aging to a suitable viscosity to obtain a transparent spinnable sol. Under any conditions, gel fibers can be prepared by centrifugal spinning. The gel fiber was heated to 450°C at a rate of 1°C/min and kept for 1 hour. Then it was heated to 650°C at a rate of 1°C/min and kept for 2 hours. Then it was heated to 800°C at a rate of 10°C/min and kept for 2 hours. , to obtain γ-A1 ₂ O ₃ fiber. After the fiber is naturally cooled to room temperature, it is directly placed in a high-temperature furnace preheated to 1200°C and calcined for 1 hour to obtain α-A1 2 O 3 fiber with zinc oxide crystal nucleation points 2 loaded on the surface. A1 ₂ O ₃ continuous fiber 1 (Figure 1, 2).

S2. Growth method of zinc oxide nanorods on the surface of continuous alumina fibers

Weigh 1.54g of hexamethylphosphophthaletriamine (C ₆ H ₁₈ N ₃ OP), add 110 mL of deionized water, continue stirring and slowly add 3.28g of zinc nitrate hexahydrate (Zn(NO ₃ ) ₂ ·6H ₂ O ), stir continuously for 24 hours at room temperature to prepare the required columnar zinc oxide growth solution.

Weigh a certain amount of alumina continuous fiber 1 and put it into a high-temperature reaction device lined with polytetrafluoroethylene. Add zinc oxide growth solution and keep it at 100°C for 10 hours. After cooling to room temperature, let it stand for 10 hours. Then take out the oxide growth solution. The aluminum continuous fiber 1 is washed several times with water and ethanol to remove excess solvent and zinc oxide. Finally, the aluminum oxide connected fiber is transferred to an oven and dried at 75°C for 20 minutes to obtain zinc oxide nanorods grown on the surface. 3 arrays of continuous alumina fibers with efficient antibacterial photocatalytic functions (Figures 3 and 4).

Example 2:

A method for preparing high-efficiency antibacterial photocatalytic continuous alumina fibers, which consists of continuous alumina fibers and an array of zinc oxide nanorods 3 grown on the surface. The specific steps are as follows:

S1. Preparation method of continuous alumina fiber

Aluminum salt is used as the aluminum source, wherein the aluminum salt is aluminum acetate, and the material ratio of the aluminum source to water is 1:20. Dissolve the aluminum salt in water and react at 70°C for about 16 hours. AIP is completely hydrolyzed. Use filter paper to filter the impurities to obtain a relatively clear and transparent sol.

Weigh a certain mass of zinc sulfate and add it to water, stir at 70°C until uniformly dispersed; finally, slowly add the aqueous solution containing zinc chloride to the sol containing aluminum salt, and continue stirring until a uniformly mixed sol is formed.

Mix the above sol in different proportions at room temperature, stir to mix evenly, and then place it in a 70°C water bath to age to a suitable viscosity to obtain a transparent spinnable sol. Under suitable temperature, humidity and rotational speed conditions, it can be centrifuged Gel fibers are prepared by spinning. The gel fiber was heated to 450°C at a rate of 1°C/min and kept for 1 hour. Then it was heated to 650°C at a rate of 1°C/min and kept for 2 hours. Then it was heated to 800°C at a rate of 10°C/min and kept for 2 hours. , to obtain γ-A1 ₂ O ₃ fiber. After the fiber is naturally cooled to room temperature, it is directly placed in a high-temperature furnace preheated to 1200°C and calcined for 1 hour to obtain alumina with zinc oxide nucleation points 2 loaded on the surface. Continuous fiber 1 (Figure 1, 2).

S2. Growth method of zinc oxide nanorods on the surface of continuous alumina fibers

Weigh 1.16g of cetyltrimethylammonium chloride and add 110mL of deionized water. Continue stirring and slowly add 2.46g of zinc phosphate. Continue stirring for 18 hours at room temperature to prepare the required columnar zinc oxide growth solution.

Weigh a certain amount of alumina connecting fiber 1 and put it into a high-temperature reaction device lined with polytetrafluoroethylene. Add zinc oxide growth solution and keep it at 80°C for 8 hours. After cooling to room temperature, let it stand for 10 hours. Then take out the oxide growth solution. The aluminum fiber was washed several times with water and ethanol to remove excess solvent and zinc oxide. Finally, the aluminum fiber was transferred to an oven and dried at 60°C for 40 minutes to obtain an array of zinc oxide nanorods 3 grown on the surface. Continuous alumina fiber with efficient antibacterial photocatalytic function (Figure 3, 4).

Example 3:

A method for preparing high-efficiency antibacterial photocatalytic continuous alumina fibers, which consists of continuous alumina fibers and surface-grown zinc oxide nanorod arrays. The specific steps are as follows:

S1. Preparation method of continuous alumina fiber

Aluminum salts are used as the aluminum source, where the aluminum salts are aluminum chloride and aluminum nitrate respectively, and the material ratio of the aluminum source to water is 1:10. Dissolve the aluminum salt in water and react under reflux and stirring conditions at 60°C for about 8 hours to obtain a relatively clear and transparent sol.

Weigh a certain mass of zinc sulfate and add it to water, stir at 60°C until uniformly dispersed; finally, slowly add the aqueous solution containing zinc chloride to the sol containing aluminum salt, and continue stirring until a uniformly mixed sol is formed.

Mix the above sol and basic aluminum methylacetate solution in different proportions at room temperature, stir to mix evenly, and then place it in a 60°C water bath to age to a suitable viscosity to obtain a transparent spinnable sol. Under any conditions, gel fibers can be prepared by centrifugal spinning. The gel fiber was heated to 450°C at a rate of 1°C/min and kept for 1 hour. Then it was heated to 650°C at a rate of 1°C/min and kept for 2 hours. Then it was heated to 800°C at a rate of 10°C/min and kept for 2 hours. , to obtain γ-A1 ₂ O ₃ fiber. After the fiber is naturally cooled to room temperature, it is directly placed in a high-temperature furnace preheated to 1200°C and calcined for 1 hour to obtain alumina with zinc oxide crystal nucleation points 2 loaded on the surface. Continuous fiber 1 (Figure 1, 2).

S2. Growth method of zinc oxide nanorods on the surface of continuous alumina fibers

Weigh 0.6g of tetramethylammonium bromide and add 110mL of deionized water. Continue stirring and slowly add 1.64g of zinc nitrate hexahydrate. Stir continuously for 12 hours at room temperature to prepare the required columnar zinc oxide growth solution.

Weigh a certain amount of alumina connecting fiber 1 and put it into a high-temperature reaction device lined with polytetrafluoroethylene. Add zinc oxide growth solution and keep it at 65°C for 6 hours. After cooling to room temperature, let it stand for 10 hours. Then take out the oxide growth solution. The aluminum-connected fiber 1 was washed several times with water and ethanol to remove excess solvent and zinc oxide. Finally, the alumina fiber was transferred to an oven and dried at 45°C for 60 minutes to obtain zinc oxide nanorods 3 grown on the surface. Array of continuous alumina fibers with efficient antibacterial photocatalytic function (Figure 3, 4).

The description and practice disclosed in the present invention are easy to think and understand for those of ordinary skill in the art, and several improvements and modifications can be made without departing from the principles of the present invention. Therefore, modifications or improvements made without departing from the spirit of the present invention should also be regarded as the protection scope of the present invention.

Claims (6)

1. The preparation method of the high-efficiency antibacterial photocatalytic continuous alumina fiber consists of the continuous alumina fiber and a surface-grown zinc oxide nano rod array, and is characterized by comprising the following specific steps of:

s1, preparation method of continuous alumina fiber

Taking aluminum salt and aluminum isopropoxide AIP as aluminum sources, wherein the mass ratio of the aluminum sources to water is 1:10-1:30, and the mass ratio of the aluminum salt to the aluminum isopropoxide AIP is 1:0.5-1:3; dissolving aluminum salt in water, adding AIP under reflux stirring at 60-80deg.C, reacting for 8-24 hr, completely hydrolyzing AIP, and filtering impurities with filter paper to obtain clear transparent sol;

weighing zinc salt with certain mass, adding the zinc salt into water, and stirring the mixture at the temperature of 60-80 ℃ until the zinc salt is uniformly dispersed; finally, slowly adding the sol solution containing zinc salt into the sol containing aluminum salt, and continuously stirring until a uniformly mixed sol is formed;

copper chloride CuCl ₂ ·2H ₂ O is dissolved in formic acid HCOOH and glacial acetic acid CH as catalyst ₃ Adding aluminum powder into the mixed solution of COOH and water, reacting for 4.5 hours at the temperature of 100 ℃ under the condition of reflux stirring, filtering out the replaced copper by using filter paper, and obtaining transparent basic aluminum methylacetate solution with excessive acid; wherein the ratio of the amounts of the substances of the raw materials is Al to HCOOH to CH ₃ COOH:H ₂ O＝1:4.5:3:24,Al:CuC1 ₂ ·2H ₂ O＝1:0.011；

Mixing the sol and the basic aluminum methylacetate solution in different proportions at normal temperature, stirring to uniformly mix the solutions, aging the mixture in a water bath at 80 ℃ to proper viscosity to obtain transparent spinnability sol, and preparing gel fibers by centrifugal spinning under proper temperature, humidity and rotating speed; heating gel fiber to 450 ℃ at a speed of 1 ℃/min, preserving heat for 1h, heating to 650 ℃ at a speed of 1 ℃/min, preserving heat for 2h, heating to 800 ℃ at a speed of 10 ℃/min, and preserving heat for 2h to obtain gamma-A1 ₂ O ₃ After the fiber is naturally cooled to room temperature, the fiber is directly put into a high-temperature furnace preheated to 1200 ℃ for calcination for 1h to obtain the alpha-A1 with zinc oxide crystal nucleus points loaded on the surface ₂ O ₃ Continuous fibers;

s2, growing method of zinc oxide nano rod on surface of continuous alumina fiber

Mixing ammonium salt, zinc salt and deionized water according to a certain proportion, and continuously stirring for 12-24 hours at room temperature to prepare a required rod-shaped nano zinc oxide array growth solution;

and (3) conveying the alumina continuous fiber into a reaction device, keeping the temperature of the reaction device at 65-100 ℃ for 6-10 hours, cooling the reaction device to room temperature, standing for 10 hours, repeatedly washing the alumina continuous fiber through a water tank for several times after the surface rod-shaped nano zinc oxide array grows completely to remove redundant solvents and other impurities, finally introducing the alumina fiber into a baking oven, and drying the alumina fiber for 20-60 minutes at 45-75 ℃ to obtain the high-efficiency antibacterial photocatalytic continuous alumina fiber with the surface growing zinc oxide nano rod array.

2. The method for preparing high-efficiency antibacterial photocatalytic continuous alumina fiber according to claim 1, wherein in step S1, the aluminum salt is one or a mixture of any of aluminum chloride, aluminum nitrate and aluminum acetate; the zinc salt is one or a mixture of several of zinc chloride, zinc carbonate, zinc phosphate, zinc acetate or zinc nitrate; the ammonium salt is one or more of cetyl trimethyl ammonium bromide, tetramethyl ammonium bromide, cetyl trimethyl ammonium chloride and tetradecyl trimethyl ammonium bromide.

3. The method for preparing high-efficiency antibacterial photocatalytic continuous alumina fiber according to claim 1, wherein in step S1, the doping ratio of zinc salt is 2-10 wt%.

4. The method for preparing high-efficiency antibacterial photocatalytic continuous alumina fiber according to claim 1, wherein the continuous α -A1 prepared in step S1 ₂ O ₃ The fiber diameter of the fiber is 1-10 mu m, and the fiber phase composition is alpha-Al ₂ O ₃ 、γ-Al ₂ O ₃ The fiber element composition is Al, O and Zn.

5. The method for preparing high-efficiency antibacterial photocatalytic continuous alumina fiber according to claim 1, wherein in step S2, zinc oxide crystal nuclei are uniformly distributed on the surface of the continuous alumina fiber, the diameter of the zinc oxide crystal nuclei is 5-250 nm, and the distribution ratio of the zinc oxide crystal nuclei on the surface of the continuous alumina fiber is 30-80/μm ² 。

6. The method for preparing high-efficiency antibacterial photocatalytic continuous alumina fiber according to claim 1, wherein in the step S2, the diameter of the zinc oxide nano rod is 100-500 nm, and the length of the zinc oxide nano rod is 300-1500 nm.