CN112080165A

CN112080165A - Preparation method of super-hydrophobic film material with antibacterial function

Info

Publication number: CN112080165A
Application number: CN202011016756.7A
Authority: CN
Inventors: 林华香; 龙金涛; 王绪绪; 员汝胜; 龙金林; 张子重
Original assignee: Fuzhou University
Current assignee: Fujian Fuxia Technology Co ltd
Priority date: 2020-09-24
Filing date: 2020-09-24
Publication date: 2020-12-15
Anticipated expiration: 2040-09-24
Also published as: CN112080165B

Abstract

The invention discloses a super-hydrophobic film material C with an antibacterial function_nH_2n‑1O₂M/TiO₂The preparation method of the antibacterial super-hydrophobic film comprises the steps of adding cleaned sheet metal into a fatty acid ethanol solution, stirring at a constant temperature for reaction for a period of time, adding titanium glue obtained after hydrothermal reaction, coating the obtained mixed solution on a substrate, and drying at a low temperature and a normal pressure to obtain the antibacterial super-hydrophobic film. The method has the advantages of simple and easy operation, cheap and easily obtained raw materials, small reagent pollution, good reaction repeatability, mild preparation conditions and the like, and the obtained C_nH_2n‑1O₂M/TiO₂The (M = Cu, Ag, Au, Zn and Ti) film material shows good catalytic antibacterial activity in an antibacterial experiment, and has stable performance and good cyclicity.

Description

Preparation method of super-hydrophobic film material with antibacterial function

Technical Field

The invention belongs to the field of material synthesis, and particularly relates to super-hydrophobic C with an antibacterial function_nH_2n-1O₂M/TiO₂A preparation method of (M = Cu, Ag, Au, Zn and Ti) film material.

Background

Since 1972, researchers discovered TiO₂Semiconductor photocatalysis has attracted great attention of researchers at home and abroad since water can be decomposed into hydrogen and oxygen under the irradiation of ultraviolet light. Under light conditions, the semiconductor outer layer electrons are excited to transition from the valence band to the conduction band, thereby generating electron-hole pairs. Photogenerated electron holes can directly attack bacteria, and electrons can be converted into other active species, such as: o. O₂ ^-Further oxidizing the outer membrane of the bacteria, while other oxidizing active species, e.g. OH, H₂O_2，•HO₂And electrons and holes can be generated from water, so that the inactivation of bacteria on various aspects is realized. But of TiO only₂Can only be excited by ultraviolet light, so that the use of the antibacterial performance of the catalyst in the common indoor environment is limited, the prior related patent technology is mainly based on the excitation of the ultraviolet light, and therefore, the catalyst with the efficient antibacterial function in a visible light region is designed to realize TiO₂The key to antimicrobial applications.

Due to their important role in basic research and industrial applications, superhydrophobic surfaces have potential areas in the design of many new materials and devices, including electronics, catalysis, medicine, ceramics, and the like. C_nH_2n-1O₂M/TiO₂The nanoclusters are crystalline. Because it is peculiarThe super-hydrophobic performance is great, and the self-cleaning function can be endowed to the surface of the film. Compared with the common powder catalyst, the composite film material synthesized by the invention has more outstanding performance in the aspects of catalyst recovery, recycling and the like compared with the prior art.

Disclosure of Invention

The invention aims to provide a preparation method of a super-hydrophobic film material with an antibacterial function.

In order to achieve the purpose, the invention adopts the following technical scheme:

a super-hydrophobic film material with an antibacterial function is prepared by the following steps:

1) under the condition of stirring at normal temperature, dissolving fatty acid in absolute ethyl alcohol to obtain a fatty acid ethyl alcohol solution with the concentration of 0.01-1.5 mol/L;

2) adding the cleaned 0.2 x 0.2 cm-5 x 5cm sheet metal into the fatty acid ethanol solution obtained in the step 1), then adding a magnetic stirrer, and stirring and reacting at a constant temperature of 25-60 ℃ for 3-5 days;

3) carrying out hydrothermal reaction on the titanium glue at the temperature of 120-180 ℃ for 10-24h, and then adding the titanium glue into the solution obtained in the step 2) according to the volume ratio of 1: 5;

4) uniformly coating the mixed solution obtained in the step 3) on a cleaned substrate, and drying at the low temperature of 50-120 ℃ under normal pressure to obtain a super-hydrophobic thin film material CnH_2n-1O₂M/TiO₂（M=Cu、Ag、Au、Zn、Ti）。

The fatty acid in the step 1) is any one of lauric acid, myristic acid, stearic acid and octacosanoic acid.

The metal used in the step 2) comprises copper, silver, gold, zinc and titanium.

The substrate in the step 4) comprises any one of glass, PVC (polyvinyl chloride) tubes, ceramics and organic glass.

The invention has the advantages that:

the invention reports a preparation method of a super-hydrophobic film material with an antibacterial function for the first time, which is simple and easy to implement, has cheap and easily-obtained raw materials, small reagent pollution, good reaction repeatability and preparationMild conditions and the like. Obtained C_nH_2n-1O₂M/TiO₂The film material shows good catalytic antibacterial activity in photocatalytic antibacterial, and has stable performance and good cyclicity.

Drawings

FIG. 1 is a drawing showing a thin film material C prepared in example 1₁₄H₂₇O₂Cu/TiO₂Electron micrographs of (A).

FIG. 2 is a drawing showing a thin film material C prepared in example 1₁₄H₂₇O₂Cu/TiO₂Hydrophobicity test chart (1).

FIG. 3 is a drawing showing a thin film material C prepared in example 1₁₄H₂₇O₂Cu/TiO₂Antimicrobial kinetics curve (c).

FIG. 4 is a drawing showing a thin film material C prepared in example 1₁₄H₂₇O₂Cu/TiO₂The bacteriostatic circle effect diagram.

FIG. 5 is a drawing showing a thin film material C prepared in example 1₁₄H₂₇O₂Cu/TiO₂The antibacterial stability chart of (1).

FIG. 6 shows a thin film material (CH) prepared in example 2₃(CH₂)₁₂COO)₂Zn/TiO₂The real object diagram of (1).

FIG. 7 shows a thin film material (CH) prepared in example 2₃(CH₂)₁₂COO)₂Zn/TiO₂Hydrophobicity test chart (1).

FIG. 8 shows a thin film material (CH) prepared in example 2₃(CH₂)₁₂COO)₂Zn/TiO₂Antimicrobial kinetics curve (c).

Detailed Description

In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.

The titanium glue used in the embodiment is prepared by adopting a sol-gel method, and the method comprises the following specific steps: 15mL of butyl titanate was added dropwise to 100mL of anhydrous ethanol with stirring, then 100mL of water and 3mL of concentrated hydrochloric acid were added, and the mixture was cooled at room temperatureStirring for 4 days to obtain TiO₂And (3) sol.

Example 1

Placing a copper sheet which is cleaned by acetone, absolute ethyl alcohol and 0.1M hydrochloric acid solution in sequence and has the size of 3.5cm multiplied by 3.5cm into 100mL of 0.03mol/L myristic acid ethyl alcohol solution, adding a magnetic stirrer for stirring, keeping the stirring speed at 350-500r/min, and reacting for 2-5 days at the normal temperature of 25 ℃ to obtain a metal alcohol solution; pouring the titanium glue into a 50mL reaction kettle with a polytetrafluoroethylene lining, then putting the reaction kettle into an oven, and carrying out hydrothermal reaction for 12h at 160 ℃; adding 20mL of hydrothermal titanium glue into the metal alcohol solution, and uniformly stirring; coating the obtained mixed solution on a clean glass slide, and drying in an oven at normal pressure and 60 ℃ to obtain the self-cleaning super-hydrophobic film material C with the antibacterial function₁₄H₂₇O₂Cu/TiO₂. The resulting sample is shown in FIG. 1.

1. Hydrophobicity test

The hydrophobicity of the film is measured by measuring the contact angle of the film surface to water. The contact angle of the film surface with water was measured by the sessile drop method on a contact angle meter model OCA20, manufactured by Dataphysics Instruments Gmbh, germany, and the volume of the water drop was 5 μ L. As shown in fig. 2, the contact angle of the film obtained in example 1 to water is 134 °, which indicates that it has good hydrophobicity.

2. Antimicrobial kinetics test

Coli strains were cultured in MH (mueller hinton) broth at 37 ℃ for 18h and immediately diluted with PBS solution to give a final bacterial concentration of 10^8~9cfu/ml. Throughout the experiment, all glassware and PBS solutions were rinsed with deionized water and autoclaved for 20 minutes at 121 ℃ in high pressure steam. Taking 4mL of 10^8~9The cfu/mL bacterial solution is transferred to a reactor, and PBS solution is added to dilute the solution to 40mL (the concentration of the bacterial solution is about 10 in the case)^6~7cfu/ml). 2cm × 2cm of the film obtained in example 1 was added to a reactor and magnetons were added thereto at a constant rotation speed of 300r/min to bring the film into sufficient contact with the bacterial solution. Starting a xenon lamp (lambda is more than or equal to 400 nm), starting a fan to react, taking 0.5mL of bacterial liquid at equal intervals, and adding 4.5mL of PBS solutionAnd diluting the bacteria liquid by a certain multiple according to the experiment requirement in a small test tube, transferring the bacteria liquid to a dry and clean culture dish, pouring a certain amount of nutrient agar subjected to autoclaving treatment into each culture dish containing the bacteria liquid, and shaking the culture dish to uniformly disperse the bacteria liquid in the agar in a liquid state. And (3) putting the cooled and solidified nutrient agar plate into a constant-temperature shaking table at 37 ℃, culturing for 24h, reading the colony number in the plate, and analyzing data. As shown in FIG. 3, after 3.5h of visible light irradiation, the antibacterial efficiency of the film reaches 99.9%.

3. Zone of inhibition experiment

Coli strains were cultured in MH (mueller hinton) broth at 37 ℃ for 18h and immediately diluted with PBS solution to give a final bacterial concentration of 10^6.5~7.5cfu/ml. Throughout the experiment, all glassware and PBS solutions were rinsed with deionized water and autoclaved for 20 minutes at 121 ℃ in high pressure steam. Taking 0.5ml of 10^6.5~7.5The bacterial solution of cfu/ml is uniformly dispersed on a freshly prepared nutrient agar plate, after standing for five minutes, the film obtained in the example 1 with the size of 1cm multiplied by 1cm is placed at the center of the nutrient agar plate, a xenon lamp light source (the wavelength is more than or equal to 400 nm) is used for irradiating for 2 hours, then the film is cultured in a constant temperature incubator at 37 ℃ for 24 hours, and a bacteriostatic circle test experiment is carried out, wherein the result is shown in figure 4 (the marked circle in figure 4 represents the size of the bacteriostatic circle).

4. Antimicrobial stability test

Coli strains were cultured in MH (mueller hinton) broth at 37 ℃ for 18h and immediately diluted with PBS solution to give a final bacterial concentration of 10^8~9cfu/ml. Throughout the experiment, all glassware and PBS solutions were rinsed with deionized water and autoclaved for 20 minutes at 121 ℃ in high pressure steam. Taking 4mL of 10^8~9cfu/mL of the bacterial solution is transferred to a reactor, and the solution is diluted to 40mL by adding PBS (the concentration of the bacterial solution is about 10 at this time)^6~7cfu/ml). 2cm × 2cm of the film obtained in example 1 was added to a reactor and magnetons were added thereto at a constant rotation speed of 300r/min to bring the film into sufficient contact with the bacterial solution. Turning on xenon lamp (lambda is more than or equal to 400 nm), turning on fan to react at equal intervalsAdding 0.5mL of bacterial liquid into a small test tube containing 4.5mL of PBS solution, diluting the bacterial liquid by a certain multiple according to experiment requirements, transferring the bacterial liquid to a dry and clean culture dish, pouring a certain amount of nutrient agar subjected to autoclaving treatment into each culture dish containing the bacterial liquid, and shaking the culture dish to uniformly disperse the bacterial liquid in the liquid agar. And (3) putting the cooled and solidified nutrient agar plate into a constant-temperature shaking table at 37 ℃, culturing for 24h, reading the colony number in the plate, and analyzing data. The catalyst after the reaction was filtered, washed and dried, and then the experiment was repeated as described above. The kinetic curves of the four reactions are shown in FIG. 5.

Example 2

Putting a zinc sheet which is cleaned by acetone, absolute ethyl alcohol and 0.1M hydrochloric acid solution and has the size of 3.5cm multiplied by 3.5cm into 100mL of 0.03mol/L octadecanoic acid ethanol solution, adding a magnetic stirrer for stirring, keeping the stirring speed at 350-500r/min, and reacting for 2-5 days at the normal temperature of 25 ℃ to obtain a metal alcohol solution; pouring the titanium glue into a 50mL reaction kettle with a polytetrafluoroethylene lining, then putting the reaction kettle into an oven, and carrying out hydrothermal reaction for 12h at 160 ℃; adding 20mL of hydrothermal titanium glue into the metal alcohol solution, and uniformly stirring; coating the obtained mixed solution on a clean glass slide, and drying in an oven at normal pressure and 60 ℃ to obtain the self-cleaning super-hydrophobic film material (CH) with the antibacterial function₃(CH₂)₁₂COO)₂Zn/TiO₂. The resulting sample is shown in FIG. 6.

1. Hydrophobicity test

The hydrophobicity of the film is measured by measuring the contact angle of the film surface to water. The contact angle of the film surface with respect to water was measured by the sessile drop method on a contact angle meter model OCA20, manufactured by Datophysics Instruments Gmbh, Germany, and the volume of the water drop was 5. mu.L. As shown in fig. 7, the contact angle of the film obtained in example 2 to water was 134 °, indicating good hydrophobicity.

2. Antimicrobial kinetics test

Escherichia coli strain was cultured in MH (mueller hinton) broth at 37 ℃ for 18 hours and then immediately diluted with PBS solution to obtain bacteria having a final concentration of 10^8~9 cfu /And (3) ml. All glassware and PBS solutions were washed with deionized water and autoclaved at 121 ℃ with high pressure steam for 20 minutes throughout the experiment. Taking 4mL of 10⁸ ^~9The cfu/mL of the stock solution was transferred to a reactor and diluted to 40mL with PBS (the concentration of the stock solution was about 10)^6~7cfu/ml). The film obtained in example 2 with the thickness of 2cm multiplied by 2cm is added into a reactor and magnetons are added, and the constant rotating speed is 300r/min, so that the film catalyst can be fully contacted with the bacterial liquid. Turning on a xenon lamp (lambda is more than or equal to 400 nm), starting a fan to react, taking 0.5mL of the bacterial liquid at equal intervals, adding the bacterial liquid into a small test tube containing 4.5mL of PBS solution, diluting the bacterial liquid by a certain multiple according to experiment requirements, transferring the bacterial liquid into a dry and clean culture dish, pouring a certain amount of nutrient agar subjected to autoclaving treatment into each culture dish containing the bacterial liquid, and shaking the culture dish to uniformly disperse the bacterial liquid in the agar in a liquid state. And (3) putting the cooled and solidified nutrient agar plate into a constant-temperature shaking table at 37 ℃, culturing for 24h, reading the colony number in the plate, and analyzing data. As shown in FIG. 8, after 3h of visible light irradiation, the antibacterial efficiency of the film reaches 99.9%.

The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims

1. A preparation method of a super-hydrophobic film material with an antibacterial function is characterized by comprising the following steps: the method comprises the following steps:

1) dissolving fatty acid in absolute ethyl alcohol under the condition of stirring at normal temperature to obtain a fatty acid ethyl alcohol solution;

2) adding the cleaned sheet metal into the fatty acid ethanol solution obtained in the step 1), and stirring and reacting for a period of time at constant temperature;

3) carrying out hydrothermal reaction on the titanium glue at a certain temperature for a period of time, and then adding the titanium glue into the solution obtained in the step 2) according to the volume ratio of 1: 5;

4) uniformly coating the mixed solution obtained in the step 3) on a substrate, and drying at low temperature and normal pressure to obtain the super-hydrophobic film material.

2. The method for preparing the superhydrophobic film material with the antibacterial function according to claim 1, wherein the method comprises the following steps: the fatty acid in the step 1) is any one of lauric acid, myristic acid, stearic acid and octacosanoic acid.

3. The method for preparing the superhydrophobic film material with the antibacterial function according to claim 1, wherein the method comprises the following steps: the concentration of the fatty acid ethanol solution obtained in the step 1) is 0.01-1.5 mol/L.

4. The method for preparing the superhydrophobic film material with the antibacterial function according to claim 1, wherein the method comprises the following steps: the specification of the sheet metal in the step 2) is 0.2 multiplied by 0.2 cm-5 multiplied by 5 cm; the metal includes copper, silver, gold, zinc, and titanium.

5. The method for preparing the superhydrophobic film material with the antibacterial function according to claim 1, wherein the method comprises the following steps: and 2) carrying out constant-temperature stirring reaction at the temperature of 25-60 ℃ for 3-5 days.

6. The method for preparing the superhydrophobic film material with the antibacterial function according to claim 1, wherein the method comprises the following steps: the temperature of the hydrothermal reaction in the step 3) is 180 ℃, and the time is 12 h.

7. The method for preparing the superhydrophobic film material with the antibacterial function according to claim 1, wherein the method comprises the following steps: the substrate in the step 4) comprises any one of glass, PVC (polyvinyl chloride) tubes, ceramics and organic glass.

8. The method for preparing the superhydrophobic film material with the antibacterial function according to claim 1, wherein the method comprises the following steps: the low temperature in the step 4) is in the range of 50-120 deg.C^。C。

9. An antibacterial super-hydrophobic film material prepared by the method of claim 1.