阅读说明：本技术 一种具有分级结构的高效抗菌杀毒铜基滤网及制备方法 (Efficient antibacterial and antivirus copper-based filter screen with hierarchical structure and preparation method ) 是由 鲁启鹏 李墨影 曹文斌 刘文秀 曾丽 赵金平 于 2020-04-21 设计创作，主要内容包括：一种具有分级结构的高效抗菌杀毒铜基滤网及制备方法。抗菌铜基滤网组成为铜网骨架、在铜网表面生长的Cu(OH)<Sub>2</Sub>纳米棒阵列、在Cu(OH)<Sub>2</Sub>纳米棒表面生长的Cu基金属有机框架(简称Cu-BDC MOF,为铜-对苯二甲酸)阵列、在Cu-BDC MOF表面负载的可见光光催化剂四部分构成。生产包括铜网表面预处理、表面修饰剂的制备、金属有机框架的制备、纳米可见光光催化材料的负载四个步骤。本发明公开的一种具有分级结构的高效抗菌杀毒铜基滤网能够对细菌病毒等进行有效的灭活,保证环境水源以及生活用水的干净,保障人体健康,可以应用于防护口罩、空气净化、水体消毒等领域。(A high-efficiency antibacterial and antivirus copper-based filter screen with a hierarchical structure and a preparation method thereof. The antibacterial copper-based filter screen comprises a copper screen framework and Cu (OH) growing on the surface of the copper screen 2 Nanorod arrays in Cu (OH) 2 Surface growth of nano rodThe long Cu-based metal organic framework (Cu-BDC MOF for short) array and the visible light photocatalyst loaded on the surface of the Cu-BDC MOF are formed. The production comprises four steps of copper mesh surface pretreatment, surface modifier preparation, metal organic framework preparation and nano visible light photocatalytic material loading. The high-efficiency antibacterial and antivirus copper-based filter screen with the hierarchical structure disclosed by the invention can effectively inactivate bacteria and viruses, ensures the cleanness of environmental water sources and domestic water, ensures the health of human bodies, and can be applied to the fields of protective masks, air purification, water body disinfection and the like.)

1. A high-efficiency antibacterial and antivirus copper-based filter screen with a hierarchical structure is characterized in that microorganisms are inactivated through surface Cu-BDC MOF and a visible light photocatalyst;

the high-efficiency antibacterial and antivirus copper-based filter screen with the hierarchical structure comprises the following components:

the basic skeleton is a metal copper mesh;

cu (OH) grown on the surface of copper mesh₂A nanorod array;

in Cu (OH)₂A Cu-BDC MOF array grown on the surface of the nanorod;

a visible light photocatalyst supported on the surface of the Cu-BDC MOF;

wherein: the copper content of the copper net is C1 wt%, the impurity content is C2 wt%, and the C1/C2 is more than 99; the copper mesh ensures that the sample has enough flexibility and certain strength in the whole and simultaneously is Cu (OH)₂And a copper source of Cu-BDC MOF;

the appearance of the copper hydroxide is formed by nanorods vertically arranged on the surface of a copper mesh and grown as growth points of Cu-BDC MOF and a copper source; the copper hydroxide nanorod array can also release copper ions, and is chemically combined with biological tissues of microorganisms, so that the activity of the microorganisms is reduced;

the appearance of the Cu-BDC metal organic framework is a nano sheet which grows vertical to the copper hydroxide nano rod; the Cu-BDC metal organic framework array can release copper ions, and the copper ions are chemically combined with biological tissues of microorganisms, so that the activity of the microorganisms is reduced; penetrating the cell membrane by sharp edge cleavage; as attachment points for visible light photocatalysts;

the visible light catalyst is nanoparticles distributed on the surface of a Cu-BDC metal organic framework, and can provide superoxide radicals through a photocatalysis process to inactivate microorganisms and promote copper ion release.

2. According to claim 1The high-efficiency antibacterial and antivirus copper-based filter screen with the hierarchical structure is characterized in that the filter screen is Cu (OH)₂Nanorod arrays and Cu-BDC MOF arrays kill microbes by slowly releasing copper ions.

3. The highly effective antibacterial and antivirus copper-based filter screen with hierarchical structure as claimed in claim 1, wherein Cu (OH)₂Nanorod arrays and Cu-BDC MOF arrays kill microbes by piercing, rupturing, pulling cell membrane physical effects.

4. The copper-based screen with a hierarchical structure for highly effective antibacterial and antivirus functions as claimed in claim 1, wherein the visible light photocatalyst kills microbes by responding to superoxide radical generated by responsive light and promoting release of copper ions in addition to killing microbes directly.

5. The method for preparing the high-efficiency antibacterial and antivirus copper-based filter screen with the hierarchical structure according to claim 1, characterized by comprising the following steps:

(1) copper mesh pretreatment: pretreating the cleaned copper mesh and drying for later use;

(2) preparing a surface modifier;

(3) preparation of metal organic framework: soaking the substrate in the surface modifier, reacting at 40-70 deg.C for 10-20min, and drying at 50 deg.C;

(4) and (3) loading of the nano visible light photocatalytic material: soaking the substrate in the nano visible light photocatalytic material sol for 1min, drying at 50 ℃ and room temperature, and repeating for 3-9 times.

6. The copper-based filter screen with hierarchical structure for high-efficiency antibacterial and antivirus functions as claimed in claim 5, wherein the pretreatment step of the preparation step (1) is activation by using a mixed solution of strong base and ammonium persulfate, wherein the strong base is sodium hydroxide or potassium hydroxide or other strong alkaline reactant.

7. The highly effective antibacterial and antivirus copper-based filter screen with hierarchical structure as claimed in claim 5, wherein the preparation method of the surface modifier of the preparation step (2) is: mixing 1 volume part of N-N dimethylformamide, 8-10 volume parts of deionized water and absolute ethyl alcohol for 0-2 volumes, stirring for 2min, adding 0.002 mass part of terephthalic acid, and stirring for 2 min.

8. The highly effective antibacterial and antivirus copper-based filter screen with hierarchical structure as claimed in claim 5, wherein the preparation method of metal organic framework of preparation step (2) is: heating the surface modifier to 40-70 ℃, and soaking the copper mesh in the surface modifier for heat preservation for 10-20 min.

9. The high-efficiency antibacterial and antivirus copper-based filter screen with a hierarchical structure according to claim 5, wherein the used nano visible light photocatalytic material is one of nitrogen-doped nano titanium dioxide and tungsten-doped nano titanium dioxide.

10. The preparation method of the high-efficiency antibacterial and antivirus copper-based filter screen with the hierarchical structure as claimed in claim 1, characterized by comprising the following specific preparation steps:

(1) copper mesh pretreatment:

firstly, preparing a mixed aqueous solution with the solubility of 2.5mol/L of sodium hydroxide and the solubility of 0.13mol/L of ammonium persulfate; then immersing the copper mesh which is sequentially subjected to ultrasonic cleaning by sulfuric acid, deionized water and acetone into the solution for 30 min; rinsing with deionized water, and drying at room temperature for later use;

(2) preparation of surface modifier:

firstly, mixing 1 part by volume of N-N dimethylformamide, 8-10 parts by volume of deionized water and absolute ethyl alcohol for 0-2 volumes, stirring for 2min, adding 0.002 part by mass of terephthalic acid, and stirring for 2 min;

(3) preparation of metal organic framework:

firstly, heating the surface modifier to 40-70 ℃, and then soaking the substrate in the surface modifier for reaction for 10-20 min;

(4) and (3) loading of the nano visible light photocatalytic material:

firstly, absorbing 1 volume part of nano titanium dioxide sol responsive to visible light, adding the nano titanium dioxide sol into 5 volume parts of deionized water, stirring for 2min, then soaking a substrate in the nano visible light photocatalytic material sol for 1min, drying at 50 ℃, and repeating for 3-9 times; wherein the nano titanium dioxide sol is one of nitrogen-doped nano titanium dioxide and tungsten-doped nano titanium dioxide.

Technical Field

The invention relates to the field of environment-friendly materials, in particular to the field of air purification, water purification and antibacterial functions.

Background

With the continuous development of the times, the living standard of people is continuously improved, but many air-borne diseases still occur in recent decades, and the discomfort of people caused by the unclean domestic water still exists, so that people urgently hope that some technologies can be developed to ensure the safety and reliability of air and domestic water.

Copper and copper ions have a long history of being used as an antibacterial agent, and are broad-spectrum inorganic antibacterial and antivirus materials, and the antibacterial and antivirus mechanism of the copper and copper ions to microorganisms is a. cell membranes are damaged through contact reaction, and protein denaturation is induced; b. the generation of active oxygen inhibits the killing of microorganisms. Most of the prior methods for using the copper-based antibacterial and disinfectant materials are to disperse the materials in a re-solution for use, but the liquid antibacterial and disinfectant is inconvenient to use for air purification, and copper ions are rapidly lost along with the flow of water when the liquid antibacterial and disinfectant materials are used for disinfecting water.

The disinfection of air and domestic water puts a series of demands on antibacterial materials: a. has good permeability: the fluidity of air and domestic water requires that the antibacterial material has certain permeability and cannot block the flow of air and domestic water; b. the load is firm: the antibacterial material can bear the flowing scouring of air and water so as to achieve the effect of long-acting and durable disinfection. c. Controllable sterilization capability: the antibacterial material can be applied in different scenes and has the antibacterial capability enhanced along with the control factors.

Disclosure of Invention

Aiming at the problems and the practical application requirements, the invention discloses a high-efficiency antibacterial and antivirus copper-based filter screen with a hierarchical structure. The material is composed of a metal copper mesh framework, Cu (OH) growing on the surface of the copper mesh framework₂Nanorod arrays in Cu (OH)₂The Cu-BDC MOF array grown on the surface of the nanorod and the visible light photocatalyst loaded on the surface of the Cu-BDC MOF array are formed.

The aperture of the antibacterial and antivirus copper-based filter screen is between 20 and 30 microns, so that the air and water body flow can not be obstructed, and microorganisms in the air can be filtered and killed; the material can slowly release copper ions, and can keep the solubility of the copper ions in the solution stably and slowly released for a long time. Cu (OH) directly growing on surface of copper-based filter screen for efficient antibacterial and antivirus₂The nanorod array and the Cu-BDMOF array are firmly combined with the matrix and cannot fall off due to washing; furthermore, both arrays have sharp edges that destroy microbes by physically destroying the cell membrane. In addition, the visible light photocatalyst on the outermost layer of the copper-based filter screen can respond to visible light and generate superoxide radical to promote the release of copper ions, and the superoxide radical can also kill microbes directly. More importantly, the introduction of the photocatalyst can accelerate the slow release of copper ions in the Cu-BDC MOF, and the photocatalyst can play a role of a photoswitch. The material can combine physical inactivation effect, copper ion sterilization effect and photocatalytic inactivation effect, and exert synergistic effect to improve the inactivation efficiency of bacteria.

A high-efficiency antibacterial and antivirus copper-based filter screen with a hierarchical structure is characterized in that microorganisms are inactivated through surface Cu-BDC MOF and a visible light photocatalyst;

the high-efficiency antibacterial and antivirus copper-based filter screen with the hierarchical structure comprises the following components:

the basic skeleton is a metal copper mesh;

cu (OH) grown on the surface of copper mesh₂A nanorod array;

in Cu (OH)₂A Cu-BDC MOF array grown on the surface of the nanorod;

visible light photocatalyst loaded on the surface of Cu-BDC MOF.

Wherein: the copper content of the copper mesh is C1 wt%, the impurity content is C2 wt%, and the C1/C2 is above 99. The copper mesh ensures that the sample has enough flexibility and certain strength in the whole and simultaneously is Cu (OH)₂And a copper source of Cu-BDC MOF.

The appearance of the copper hydroxide is formed by nanorods vertically arranged on the surface of a copper mesh and grown on the surface of the copper mesh, and the nanorods are used as growth points of Cu-BDC MOF and a copper source. The copper hydroxide nanorod array can also release copper ions, and the copper ions are chemically combined with biological tissues of microorganisms, so that the activity of the microorganisms is reduced.

The appearance of the Cu-BDC metal organic framework is a nano sheet which grows vertical to the copper hydroxide nano rod. The Cu-BDC metal organic framework array can release copper ions, and the copper ions are chemically combined with biological tissues of microorganisms, so that the activity of the microorganisms is reduced; penetrating the cell membrane by sharp edge cleavage; as attachment points for visible light photocatalysts.

The visible light catalyst is nanoparticles distributed on the surface of a Cu-BDC metal organic framework, and can provide superoxide radicals through a photocatalysis process to inactivate microorganisms and promote copper ion release.

Further, Cu (OH)₂Nanorod arrays and Cu-BDC MOF arrays kill microbes by slowly releasing copper ions.

Further, Cu (OH)₂Nanorod arrays and Cu-BDC MOF arrays kill microbes by piercing, rupturing, pulling cell membrane physical effects.

Further, visible light photocatalysts kill microbes by responding to superoxide radicals generated by responsive light, which can promote the release of copper ions in addition to directly killing microbes.

The preparation method of the high-efficiency antibacterial and antivirus copper-based filter screen with the hierarchical structure comprises the following preparation steps:

(1) copper mesh pretreatment: pretreating the cleaned copper mesh and drying for later use;

(2) preparing a surface modifier;

(3) preparation of metal organic framework: soaking the substrate in the surface modifier, reacting at 40-70 deg.C for 10-20min, and drying at 50 deg.C;

(4) and (3) loading of the nano visible light photocatalytic material: soaking the substrate in the nano visible light photocatalytic material sol for 1min, drying at 50 ℃ and room temperature, and repeating for 3-9 times.

Further, the pretreatment step in the preparation step (1) is activation by using a mixed solution of strong base and ammonium persulfate, wherein the strong base is other strong-base reactants such as sodium hydroxide or potassium hydroxide.

Further, the preparation method of the surface modifier in the preparation step (2) comprises the following steps: mixing 1 volume part of N-methylformamide, 8-10 volume parts of deionized water and absolute ethyl alcohol for 0-2 volumes, stirring for 2min, adding 0.002 mass part of terephthalic acid, and stirring for 2 min.

Further, the preparation method of the metal organic framework in the preparation step (2) comprises the following steps: heating the surface modifier to 40-70 ℃, and soaking the copper mesh in the surface modifier for heat preservation for 10-20 min.

Furthermore, the used nano visible light photocatalysis material is one of nitrogen-doped nano titanium dioxide and tungsten-doped nano titanium dioxide.

A preparation method of a high-efficiency antibacterial and antivirus copper-based filter screen with a hierarchical structure comprises the following specific preparation steps:

(1) copper mesh pretreatment:

firstly, preparing a mixed aqueous solution with the solubility of 2.5mol/L of sodium hydroxide and the solubility of 0.13mol/L of ammonium persulfate; then immersing the copper mesh which is sequentially subjected to ultrasonic cleaning by sulfuric acid, deionized water and acetone into the solution for 30 min; rinsing with deionized water, and drying at room temperature for later use.

(2) Preparation of surface modifier:

firstly, mixing 1 volume part of N-N dimethylformamide, 8-10 volume parts of deionized water and absolute ethyl alcohol by a volume ratio of 0-2, stirring for 2min, adding 0.002 mass part of terephthalic acid, and stirring for 2 min.

(3) Preparation of metal organic framework:

firstly, the surface modifier is heated to 40-70 ℃, and then the substrate is soaked in the surface modifier for reaction for 10-20 min.

(4) And (3) loading of the nano visible light photocatalytic material:

firstly, 1 volume part of nano titanium dioxide sol (one of nitrogen-doped nano titanium dioxide and tungsten-doped nano titanium dioxide) with visible light response is absorbed and added into 5 volume parts of deionized water, the mixture is stirred for 2min, then a substrate is soaked in the nano visible light photocatalytic material sol for 1min, and then the drying is carried out at 50 ℃, and the steps are repeated for 3-9 times.

The invention overcomes the defects of the prior art, independently develops the high-efficiency antibacterial and antivirus copper-based filter screen with a hierarchical structure by preparing an in-situ growth preparation method, solves the problems that the antibacterial and antivirus of the water body of the disinfectant is lost along with the flowing of the water body and can not achieve long-term sterilization, and utilizes the characteristic of permeability of the copper screen to ensure that the copper screen can not obstruct the flowing of air and water during the disinfection. Cu (OH) based on autonomous preparation₂The nanorod array and the Cu-BDC MOF array can slowly release Cu ions and have a physical inactivation effect, the loaded visible light photocatalyst can promote the release of the Cu ions and provide a photocatalytic inactivation effect, the physical inactivation effect and the photocatalytic inactivation effect are combined, a synergistic effect is exerted, the inactivation efficiency of bacteria is improved, and therefore the high-efficiency antibacterial and antivirus copper-based filter screen with the hierarchical structure is prepared.

Drawings

Fig. 1 is a scanning electron microscope picture of the highly effective antibacterial and antivirus copper-based filter screen with a hierarchical structure prepared in example 1. A is a 200-time graph, B is a 5000-time graph, the three-dimensional structure of the material is clear, and the metal organic framework grows on the surface of the matrix uniformly.

Fig. 2 is an X-ray photoelectron spectrum of the highly effective antibacterial sterilizing copper-based filter screen having a hierarchical structure prepared in example 2. From which the peaks of Ti 2p and Cu 2p can be clearly seen.

Fig. 3 is an antibacterial effect diagram of the highly effective antibacterial and sterilizing copper-based filter screen having the hierarchical structure prepared in example 3. A and B are staphylococcus aureus treated by the sample wafer for 0h and 1 h; c and D are Escherichia coli treated by the sample piece for 0 and 1h, and the test of the antibacterial performance of the sample piece is carried out according to the test method and evaluation of the antibacterial performance of the photocatalytic material and the product under the irradiation of the visible light of GB/T30706-. As can be seen from the figure, the colony numbers of staphylococcus aureus and escherichia coli are greatly reduced after the sample wafer is illuminated for 1h, the total antibacterial property of the sample wafer is more than 99.9% according to the calculation method in the national standard, and the prepared antibacterial coating has a good antibacterial effect.

Detailed Description