CN112080165B

CN112080165B - A kind of preparation method of superhydrophobic film material with antibacterial function

Info

Publication number: CN112080165B
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: 2021-06-22
Anticipated expiration: 2040-09-24
Also published as: CN112080165A

Abstract

The invention discloses a preparation method of a super-hydrophobic thin film material C _n H _2n-1 O ₂ M/TiO ₂ (M=Cu, Ag, Au, Zn, Ti) with antibacterial function, belonging to the technical field of material synthesis. The cleaned sheet metal is added to the fatty acid ethanol solution, stirred and reacted at a constant temperature for a period of time, and the titanium glue after hydrothermal reaction is added, and then the obtained mixed solution is coated on the substrate, and dried at low temperature and normal pressure to obtain The superhydrophobic film with antibacterial function. The method is simple and easy to operate, cheap and easy to obtain raw materials, and has the advantages of less reagent pollution, good reaction repeatability, mild preparation conditions, etc. The obtained C _n H _2n-1 O ₂ M/TiO ₂ (M=Cu, Ag, Au, Zn, Ti) thin films showed good catalytic antibacterial activity in antibacterial experiments, with stable performance and good cyclability.

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 TiO₂Can realize the decomposition of water into hydrogen and oxygen under the irradiation of ultraviolet light, and the semiconductor photocatalysis has greatly led to the domestic and foreign fieldsIntense interest to researchers. 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 of the special super-hydrophobic property, 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 the super-hydrophobic film material with the antibacterial function for the first time, which is simple and easy to implement, has cheap and easily-obtained raw materials, and has the advantages of small reagent pollution, good reaction repeatability, mild preparation 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: adding 15mL of butyl titanate dropwise into 100mL of anhydrous ethanol under the stirring condition, then adding 100mL of water and 3mL of concentrated hydrochloric acid, and continuing stirring at room temperature 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. Turning on 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, 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. 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 ^~7.5cfu/ml of bacterial solution, allUniformly dispersing on a freshly prepared nutrient agar plate, standing for five minutes, placing the film with the size of 1cm multiplied by 1cm obtained in the example 1 at the midpoint of the nutrient agar plate, irradiating for 2 hours by using a xenon lamp light source (the wavelength is more than or equal to 400 nm), then culturing for 24 hours in a constant temperature incubator at 37 ℃, and carrying out a bacteriostatic circle test experiment, 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 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, 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 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, reacting for 2-5 days at the normal temperature of 25 ℃, and obtaining the metal alcohol solution(ii) a 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 10^8~9cfu/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 10^8~9The 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. Placing the cooled and solidified nutrient agar plate into a constant-temperature shaking table at 37 DEG CAfter 24h incubation, the number of colonies in the plate was read and data analysis was performed. 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 the superhydrophobic film material with antibacterial function, is characterized in that: comprise the steps:

1) Under normal temperature stirring, the fatty acid is dissolved in absolute ethanol to obtain a fatty acid ethanol solution;

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

3) Hydrothermally react the titanium glue at a certain temperature for a period of time, and then add it to the solution obtained in step 2) in a volume ratio of 1:5;

4) uniformly coating the mixed solution obtained in step 3) on the substrate, and drying at low temperature and normal pressure to obtain the superhydrophobic film material;

The metals used are copper, zinc or titanium.

2. The method for preparing a superhydrophobic film material with antibacterial function according to claim 1, wherein the fatty acid in step 1) is dodecanoic acid, tetradecanoic acid, octadecanoic acid, 20 Any of the octa acids.

3 . The method for preparing a superhydrophobic film material with antibacterial function according to claim 1 , wherein the concentration of the fatty acid ethanol solution obtained in step 1) is 0.01-1.5 mol/L. 4 .

4 . The method for preparing a superhydrophobic thin film material with antibacterial function according to claim 1 , wherein in step 2) the size of the sheet metal is 0.2×0.2cm~5×5cm. 5 .

5. The method for preparing a superhydrophobic thin film material with antibacterial function according to claim 1, characterized in that: in step 2) the temperature of the constant temperature stirring reaction is 25-60°C, and the time is 3-5 days .

6 . The method for preparing a superhydrophobic film material with antibacterial function according to claim 1 , wherein the temperature of the hydrothermal reaction in step 3) is 180° C. and the time is 12 h. 7 .

7 . The method for preparing a superhydrophobic film material with antibacterial function according to claim 1 , wherein the substrate in step 4) comprises any one of glass, PVC pipe, ceramics, and plexiglass. 8 . kind.

8 . The method for preparing a superhydrophobic thin film material with antibacterial function according to claim 1 , wherein the temperature range of the low temperature in step 4) is 50-120° C. 9 .

9. A superhydrophobic film material with antibacterial function prepared by the method of claim 1.