阅读说明：本技术 一种抗菌复合纳米纤维膜及其制备方法和应用 (Antibacterial composite nanofiber membrane and preparation method and application thereof ) 是由 汪滨 孙志明 李秀艳 王杰 娄耀元 杜宗玺 于 2019-11-05 设计创作，主要内容包括：本发明涉及抗菌纤维材料技术领域,尤其涉及一种抗菌复合纳米纤维膜及其制备方法和应用。本发明提供的抗菌复合纳米纤维膜,包括基底和基底表面的抗菌复合纳米纤维；所述抗菌复合纳米纤维包括HNTs-Ag<Sub>3</Sub>PO<Sub>4</Sub>复合颗粒和纳米纤维；所述纳米纤维为聚丙烯腈纳米纤维、热塑性弹性体聚氨酯纳米纤维或聚醚砜纳米纤维；所述HNTs-Ag<Sub>3</Sub>PO<Sub>4</Sub>复合颗粒包括改性埃洛石纳米管和负载在所述改性埃洛石纳米管表面的磷酸银。本发明提供的抗菌复合纳米纤维膜具有长效的抗菌性能和很好的空气过滤性能。(The invention relates to the technical field of antibacterial fiber materials, in particular to an antibacterial composite nanofiber membrane and a preparation method and application thereof. The antibacterial composite nanofiber membrane provided by the invention comprises a substrate and antibacterial composite nanofibers on the surface of the substrate; the antibacterial composite nanofiber comprises HNTs-Ag 3 PO 4 Composite particles and nanofibers; what is needed isThe nano-fiber is polyacrylonitrile nano-fiber, thermoplastic elastomer polyurethane nano-fiber or polyether sulfone nano-fiber; the HNTs-Ag 3 PO 4 The composite particles comprise modified halloysite nanotubes and silver phosphate loaded on the surfaces of the modified halloysite nanotubes. The antibacterial composite nanofiber membrane provided by the invention has long-acting antibacterial performance and good air filtering performance.)

1. An antibacterial composite nanofiber membrane is characterized by comprising a substrate and antibacterial composite nanofibers on the surface of the substrate;

the antibacterial composite nanofiber comprises HNTs-Ag ₃PO ₄Composite particles and nanofibers;

the nano-fiber is polyacrylonitrile nano-fiber, thermoplastic elastomer polyurethane nano-fiber or polyether sulfone nano-fiber;

the HNTs-Ag ₃PO ₄The composite particles comprise modified halloysite nanotubes and silver phosphate loaded on the surfaces of the modified halloysite nanotubes.

2. The antimicrobial composite nanofiber membrane of claim 1, wherein said HNTs-Ag ₃PO ₄The mass ratio of the composite particles to the nano fibers is (10-30): 100.

3. the antibacterial composite nanofiber membrane of claim 1 or 2, wherein the HNTs-Ag ₃PO ₄The mass ratio of the modified halloysite nanotube to the silver phosphate in the composite particles is 100: (30-100).

4. The method for preparing the antibacterial composite nanofiber membrane as claimed in any one of claims 1 to 3, characterized by comprising the steps of:

mixing the nanofiber source solution with HNTs-Ag ₃PO ₄Mixing the composite particles to obtain a spinning solution;

and (3) taking non-woven fabric as a substrate, and carrying out electrostatic spinning on the spinning solution to obtain the antibacterial composite nanofiber membrane.

5. The method of claim 4, wherein the nanofiber source solution is a polyacrylonitrile solution, a thermoplastic elastomer polyurethane solution, or a polyethersulfone solution;

the mass concentration of the polyacrylonitrile solution is 8-15%, and the solvent is N, N-dimethylformamide;

the mass concentration of the thermoplastic elastomer polyurethane solution is 15-18%, and the solvent is a mixed solution of N, N-dimethylformamide and acetone;

the mass concentration of the polyether sulfone solution is 10-18%, and the solvent is dichloromethane.

6. The method of claim 4, wherein the electrospinning is carried out using multi-spinneret spinning;

the electrostatic spinning process comprises the following steps: respectively injecting the spinning solution into a plurality of injectors, installing the injectors on a spinning machine, adjusting the advancing speed and the spinning distance of the spinning solution, and performing electrostatic spinning;

the number of the spinning nozzles for spinning by the multiple spinning nozzles is 2-10.

7. The method according to claim 4 or 6, wherein the temperature of the electrospinning is 50 to 60 ℃, and the electrostatic voltage of the electrospinning is 15 to 22 kV; the electrostatic spinning time is 1-5 h.

8. The method of claim 6, wherein the spinning solution is advanced at a speed of 0.8mL/h and the spinning distance is 15 cm.

9. The method of claim 4, wherein the HNTs-Ag is ₃PO ₄A method of making a composite particle comprising the steps of:

mixing the halloysite nanotube, deionized water, toluene and a silane coupling agent, and modifying to obtain a modified halloysite nanotube;

mixing the modified halloysite nanotube and Na ₂HPO ₄·12H ₂Mixing O, ethylene glycol and dimethyl sulfoxide to obtain a solution B;

mixing silver nitrate solution, glycol and dimethyl sulfoxide to obtain solution A;

mixing the solution A and the solution B, and loading to obtain the HNTs-Ag ₃PO ₄Composite particles.

10. Use of the antibacterial composite nanofiber membrane of any one of claims 1 to 3 or the antibacterial composite nanofiber membrane prepared by the preparation method of any one of claims 4 to 9 in preparing an air purification material.

Technical Field

The invention relates to the technical field of antibacterial fiber materials, in particular to an antibacterial composite nanofiber membrane and a preparation method and application thereof.

Background

Haze is one of the main factors influencing the air pollution problem at present, and the most main component in haze is just PM 2.5. PM2.5 refers to particles with aerodynamic diameter less than or equal to 2.5 μm in the atmosphere, which are easily inhaled into human lungs and easily cause respiratory diseases, and the surfaces of the particles are easily carried with microorganisms such as bacteria and viruses which are harmful to human health.

At present, the most effective method for treating PM2.5 in the air is to filter and intercept PM2.5 in the indoor air and kill bacteria at the same time by using a high-efficiency air filtering material with an antibacterial function, so that diseases caused by PM2.5 to human beings are reduced. However, how to improve the air filtration performance and the long-lasting antibacterial performance at the same time is a problem which needs to be continuously researched and discussed.

Disclosure of Invention

The invention aims to provide an antibacterial composite nanofiber membrane as well as a preparation method and application thereof.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides an antibacterial composite nanofiber membrane, which comprises a substrate and antibacterial composite nanofibers on the surface of the substrate;

the antibacterial composite nanofiber comprises HNTs-Ag ₃PO ₄Composite particles and nanofibers;

the nano-fiber is polyacrylonitrile nano-fiber, thermoplastic elastomer polyurethane nano-fiber or polyether sulfone nano-fiber;

the HNTs-Ag ₃PO ₄The composite particles comprise modified halloysite nanotubes and silver phosphate loaded on the surfaces of the modified halloysite nanotubes.

Preferably, the HNTs-Ag ₃PO ₄The mass ratio of the composite particles to the nano fibers is (10-30): 100.

preferably, the HNTs-Ag ₃PO ₄The mass ratio of the modified halloysite nanotube to the silver phosphate in the composite particles is 100: (30-100).

The invention also provides a preparation method of the antibacterial composite nanofiber membrane, which comprises the following steps:

mixing the nanofiber source solution with HNTs-Ag ₃PO ₄Mixing the composite particles to obtain a spinning solution;

and (3) taking non-woven fabric as a substrate, and carrying out electrostatic spinning on the spinning solution to obtain the antibacterial composite nanofiber membrane.

Preferably, the nanofiber source solution is a polyacrylonitrile solution, a thermoplastic elastomer polyurethane solution or a polyether sulfone solution;

the mass concentration of the polyacrylonitrile solution is 8-15%, and the solvent is N, N-dimethylformamide;

the mass concentration of the thermoplastic elastomer polyurethane solution is 15-18%, and the solvent is a mixed solution of N, N-dimethylformamide and acetone;

the mass concentration of the polyether sulfone solution is 10-18%, and the solvent is dichloromethane.

Preferably, the electrostatic spinning adopts multi-spinneret spinning;

the electrostatic spinning process comprises the following steps: respectively injecting the spinning solution into a plurality of injectors, installing the injectors on a spinning machine, adjusting the advancing speed and the spinning distance of the spinning solution, and performing electrostatic spinning;

the number of the spinning nozzles for spinning by the multiple spinning nozzles is 2-10.

Preferably, the temperature of the electrostatic spinning is 50-60 ℃, and the electrostatic voltage of the electrostatic spinning is 15-22 kV; the electrostatic spinning time is 1-5 h.

Preferably, the advancing speed of the spinning solution is 0.8mL/h, and the spinning distance is 15 cm.

Preferably, the HNTs-Ag ₃PO ₄A method of making a composite particle comprising the steps of:

mixing the halloysite nanotube, deionized water, toluene and a silane coupling agent, and modifying to obtain a modified halloysite nanotube;

mixing the modified halloysite nanotube and Na ₂HPO ₄·12H ₂Mixing O, ethylene glycol and dimethyl sulfoxide to obtain a solution B;

mixing silver nitrate solution, glycol and dimethyl sulfoxide to obtain solution A;

mixing the solution A and the solution B, and loading to obtain the HNTs-Ag ₃PO ₄Composite particles.

The invention also provides the application of the antibacterial composite nanofiber membrane in the technical scheme or the antibacterial composite nanofiber membrane prepared by the preparation method in the technical scheme in the preparation of air purification materials.

The invention provides an antibacterial composite nanofiber membrane, which comprises a substrate and antibacterial composite nanofibers on the surface of the substrate; the antibacterial composite nanofiber comprises HNTs-Ag ₃PO ₄Composite particles and nanofibers; the nanofiber is Polyacrylonitrile (PAN) nanofiber, thermoplastic elastomer polyurethane (TPU) nanofiber or polyether sulfone (PES) nanofiber; the HNTs-Ag ₃PO ₄The composite particles comprise modified halloysite nanotubes and silver phosphate loaded on the surfaces of the modified halloysite nanotubes. Halloysite Nanotubes (HNTs) are natural tubular clay minerals with good chemical and thermal stability, large specific surface area and abundant hydroxyl groups, and are used for selective chemical modification and in-situ Ag loading ₃PO ₄Excellent conditions are provided; the modified halloysite nanotubes are further increasedThe object loading amount of the silver phosphate effectively inhibits the agglomeration of silver phosphate nano particles, so that the silver phosphate with antibacterial property can be better dispersed on the surfaces of HNTs, and the antibacterial property is improved; meanwhile, the hollow tubular structure of the halloysite nanotube can increase the filtration efficiency of the composite nanofiber membrane without increasing the filtration resistance.

The invention also provides a preparation method of the antibacterial composite nanofiber membrane, which comprises the following steps: mixing polyacrylonitrile solution and HNTs-Ag ₃PO ₄Mixing the composite particles to obtain a spinning solution; and (3) taking non-woven fabric as a substrate, and carrying out electrostatic spinning on the spinning solution to obtain the antibacterial composite nanofiber membrane. The electrostatic spinning can be used for preparing a fiber membrane with high porosity and controllable pore diameter, and polyacrylonitrile solution and HNTs-Ag ₃PO ₄The fiber membrane obtained by mixing the composite particles and carrying out electrostatic spinning has larger specific surface area and better filtering performance.

Drawings

FIG. 1 shows Ag obtained in example 1 ₃PO ₄SEM image (a) and particle size distribution histogram (b);

FIG. 2 shows modified halloysite nanotubes (a) prepared in example 1 and HNTs-Ag prepared in example 1 ₃PO ₄SEM image of composite particle (b);

FIG. 3 shows a halloysite nanotube, a modified halloysite nanotube prepared in example 1, and HNTs-Ag prepared in example 1 ₃PO ₄Composite particles and Ag prepared in example 1 ₃PO ₄XRD pattern of the particles;

FIG. 4 shows Ag obtained in example 1 ₃PO ₄Ultraviolet-visible diffuse reflectance absorption spectra of particles (a) and [ F (R) hv] ^1/2-hv plot (b);

FIG. 5 is an infrared spectrum of a modified halloysite nanotube prepared according to example 1;

FIG. 6 is a thermogravimetric plot (a) and a differential thermogram (b) of a halloysite nanotube and the modified halloysite nanotube prepared in example 1;

FIG. 7 shows a preparation of comparative example 7Prepared Ag ₃PO ₄XRD patterns of PAN fiber membranes, m-HNTs-PAN prepared in comparative example 4 and antibacterial composite nanofiber membranes prepared in example 3;

fig. 8 is a SEN diagram (a) and a diameter distribution histogram (b) of a pure PAN fiber membrane prepared in comparative example 1, an SEM diagram (c) and a diameter distribution histogram (d) of an antibacterial composite nanofiber membrane prepared in example 1, and an SEM diagram (e) of an antibacterial composite nanofiber membrane prepared in example 3;

FIG. 9 is an infrared spectrum of a pure PAN fiber membrane (a) prepared in comparative example 1 and antibacterial composite nanofiber membranes (b-d) prepared in examples 1-3;

FIG. 10 is a TG curve of the pure PAN fiber membrane prepared in comparative example 1 and the antibacterial composite nanofiber membranes prepared in examples 1-3;

FIG. 11 is N of the pure PAN fiber membrane prepared in comparative example 1 and the antibacterial composite nanofiber membrane prepared in example 3 ₂Adsorption/desorption curves;

fig. 12 is a pore size distribution diagram of a pure PAN fiber membrane prepared in comparative example 1 and an antibacterial composite nanofiber membrane prepared in example 3;

FIG. 13 is a graph of the filtration efficiency of the pure PAN fiber membrane prepared in comparative example 1 and the antibacterial composite nanofiber membranes prepared in examples 1-3 as a function of the aerosol particle size;

FIG. 14 is a graph of the pressure drop of the pure PAN fiber membrane prepared in comparative example 1 and the antibacterial composite nanofiber membranes prepared in examples 1-3 as a function of the aerosol particle size;

FIG. 15 is a graph of the quality factor of the pure PAN fiber membrane prepared in comparative example 1 and the antibacterial composite nanofiber membranes prepared in examples 1-3 as a function of the aerosol particle size;

FIG. 16 is a graph of the filtration efficiency and filtration pressure drop of the pure PAN fiber membranes prepared in comparative example 1 and the antibacterial composite nanofiber membranes prepared in examples 1-3 as a function of gas flow rate;

FIG. 17 shows HNTs-Ag obtained from example 1 ₃PO ₄Composite particles (a), Ag prepared in example 1 ₃PO ₄A zone of inhibition picture of particles (b) and halloysite nanotubes (c);

FIG. 18 is a graph of the inhibition zones of the antibacterial composite nanofiber membranes prepared in examples 4-6 against different strains under the illumination condition (a is example 4, Escherichia coli; b is example 5, Escherichia coli; c is example 6, Escherichia coli; d is example 4, Staphylococcus aureus; e is example 5, Staphylococcus aureus; f is example 6, Staphylococcus aureus);

FIG. 19 is a graph of the inhibition zones of the antibacterial composite nanofiber membranes prepared in examples 4-6 against different strains in the dark (a is example 4, Escherichia coli; b is example 5, Escherichia coli; c is example 6, Escherichia coli; d is example 4, Staphylococcus aureus; e is example 5, Staphylococcus aureus; f is example 6, Staphylococcus aureus);

FIG. 20 is a picture of the zone of inhibition of Staphylococcus aureus by the antibacterial composite nanofiber membranes prepared in examples 1-3 under different illumination conditions (a is example 1, illumination condition; b is example 2, illumination condition; c is example 3, illumination condition; d is example 1, dark condition; e is example 2, dark condition; f is example 3, dark condition);

FIG. 21 is a photograph showing the zone of inhibition of Escherichia coli by the antibacterial composite nanofiber membranes prepared in examples 1 to 6 under illumination (a is example 4; b is example 5; c is example 6; d is example 1; e is example 2; and f is example 3);

fig. 22 is a graph of inhibition zones of the pure PAN fiber membrane prepared in comparative example 1 and the antibacterial composite nanofiber membrane prepared in example 3 against escherichia coli (b) and staphylococcus aureus (d) under natural light conditions;

fig. 23 is a graph showing the inhibition zones of the pure PAN fiber membrane prepared in comparative example 1 and the antibacterial composite nanofiber membrane prepared in example 3 against escherichia coli (b) and staphylococcus aureus (d) in the absence of light.

Detailed Description

The invention provides an antibacterial composite nanofiber membrane, which comprises a substrate and antibacterial composite nanofibers on the surface of the substrate;

the antibacterial composite nanofiber comprises HNTs-Ag ₃PO ₄Composite particles and nanofibers;

the nano-fiber is polyacrylonitrile nano-fiber, thermoplastic elastomer polyurethane nano-fiber or polyether sulfone nano-fiber;

the HNTs-Ag ₃PO ₄The composite particles comprise modified halloysite nanotubes and silver phosphate loaded on the surfaces of the modified halloysite nanotubes.

In the present invention, the substrate is preferably a PET nonwoven fabric; the diameter of the modified halloysite nanotube is preferably 10-50 nm, and the length of the modified halloysite nanotube is preferably 0.5-1 mu m; the HNTs-Ag ₃PO ₄The mass ratio of the modified halloysite nanotubes to the silver phosphate in the composite particles is preferably 100: (30-100), more preferably 100:30 or 100: 100. The invention does not have any special limitation on the size of the nano-fiber; the HNTs-Ag ₃PO ₄The mass ratio of the composite particles to the polyacrylonitrile nano-fibers is preferably (10-30): 100, more preferably (15 to 25): 100, most preferably 20: 100.

The invention also provides a preparation method of the antibacterial composite nanofiber membrane, which comprises the following steps:

mixing the nanofiber source solution with HNTs-Ag ₃PO ₄Mixing the composite particles to obtain a spinning solution;

and (3) taking non-woven fabric as a substrate, and carrying out electrostatic spinning on the spinning solution to obtain the antibacterial composite nanofiber membrane.

In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.

The invention combines nano-fiber source solution and HNTs-Ag ₃PO ₄And mixing the composite particles to obtain a spinning solution. In the invention, the nanofiber source solution is polyacrylonitrile solution, thermoplastic elastomer polyurethane solution or polyether sulfone solution; the mass concentration of the polyacrylonitrile solution is preferably 8-15%, more preferably 10%, and the solvent is preferably N, N-dimethylformamide; what is needed isThe mass concentration of the thermoplastic elastomer polyurethane solution is preferably 15 to 18 percent, more preferably 16 to 17 percent, and the solvent is preferably a mixed solution of N, N-dimethylformamide and acetone; the mass concentration of the polyether sulfone solution is preferably 10-18%, more preferably 12%, and the solvent is preferably dichloromethane.

In the present invention, the HNTs-Ag ₃PO ₄The method for preparing the composite particles preferably comprises the following steps:

mixing the halloysite nanotube, deionized water, toluene and a silane coupling agent, and modifying to obtain a modified halloysite nanotube;

mixing the modified halloysite nanotube and Na ₂HPO ₄·12H ₂Mixing O, ethylene glycol and dimethyl sulfoxide to obtain a solution B;

mixing silver nitrate solution, glycol and dimethyl sulfoxide to obtain solution A;

mixing the solution A and the solution B, and loading to obtain the HNTs-Ag ₃PO ₄Composite particles.

According to the invention, a halloysite nanotube, deionized water, toluene and a silane coupling agent are mixed and modified to obtain a modified halloysite nanotube; in the invention, the halloysite nanotube is preferably halloysite nanotube powder; the preferred particle size of the halloysite nanotube powder is 10-50 nm; the length-diameter ratio of the halloysite nanotube powder is preferably 0.5-1 mu m. In the present invention, the silane coupling agent is preferably 3-Aminopropylethoxysilane (APTES).

Before mixing, the halloysite nanotubes are preferably subjected to impurity removal and acid washing in sequence; the impurity removal is preferably: mixing the halloysite nanotube with deionized water to obtain a halloysite nanotube dispersion liquid, performing ultrasonic treatment, sucking out and throwing away a part which is precipitated in the ultrasonic halloysite nanotube dispersion liquid most quickly by using a suction pipe, performing suction filtration on the rest, and drying and grinding a solid; in the present invention, the ratio of the mass of the halloysite nanotubes to the volume of deionized water is preferably 3 g: (0-50) mL; the ultrasound is preferably carried out in an ultrasonic cell disruptor; the invention has no special limitation on the frequency of the ultrasonic wave, and the frequency well known by the person skilled in the art can be adopted; the time of the ultrasonic treatment is preferably 30 min; the invention has no special limitation on the suction filtration, drying and grinding, and can be carried out by adopting the processes well known by the technical personnel in the field. In the present invention, the acid washing is preferably: mixing the halloysite nanotube after impurity removal with a sulfuric acid solution, and carrying out acid washing; in the invention, the concentration of the sulfuric acid solution is preferably 6mol/L, and the dosage ratio of the halloysite nanotubes after impurity removal to the sulfuric acid solution is preferably 1 g: (5-20) mL, more preferably 1 g: 15 mL. In the invention, the pickling temperature is preferably 20-80 ℃, more preferably 40-70 ℃, and most preferably 70 ℃; the pickling is preferably carried out under stirring, the stirring time is preferably 2 hours, and the stirring rate is not particularly limited in the present invention and may be carried out at a rate well known to those skilled in the art. After the acid washing is finished, the invention also preferably comprises the steps of washing, filtering, drying and grinding the solid matters after the acid washing in sequence; preferably, deionized water is adopted for washing; the present invention does not have any particular limitation in the suction filtration, drying and grinding, and may be carried out by a process well known to those skilled in the art.

In the invention, the impurity removal and acid washing have the functions of removing impurity minerals and organic matters associated with the halloysite and increasing the number of surface hydroxyl groups of the halloysite, so that preparation is provided for subsequent modification of a silane coupling agent and silver phosphate loading.

In the present invention, the usage ratio of the halloysite nanotubes, deionized water, toluene and the silane coupling agent is preferably 6 g: (0-100) mL: 100mL of: (2-15) mL, more preferably 6 g: 25mL of: 100mL of: 6 mL; the halloysite nanotube, deionized water, toluene and silane coupling agent are preferably mixed, and then the silane coupling agent is added dropwise. In the present invention, the mixing of the halloysite nanotubes, deionized water and toluene is preferably performed under stirring, the stirring rate is not limited in any way, and the stirring is performed at a rate well known to those skilled in the art, and the stirring time is preferably 10 min. In the present invention, the process of dropwise addition of the silane coupling agent is preferably performed under stirring, and the stirring is not particularly limited in the present invention and may be performed by a process well known to those skilled in the art.

In the invention, the modification process is preferably reflux condensation at the temperature of 20-120 ℃ for 4-12 h under the condition of stirring, and the stirring is not limited in any way and can be carried out by adopting a process known by a person skilled in the art; the temperature of the condensation reflux is preferably 40-100 ℃, and more preferably 60-90 ℃; the time of the condensation reflux is preferably 4-10 h, and more preferably 4-6 h.

After the modification is finished, the invention preferably stands the modified liquid, takes solid substances, and washes, filters, dries and grinds the solid substances. In the invention, the washing is preferably carried out by sequentially adopting absolute ethyl alcohol and deionized water; the present invention does not have any particular limitation in the suction filtration, drying and grinding, and may be carried out by a process well known to those skilled in the art.

In the present invention, the purpose of the modification is to graft an organic functional group bearing an amine group to the halloysite surface. Therefore, on one hand, the dispersibility of the halloysite-DMF dispersion liquid in an organic solution is improved, so that a stable halloysite-DMF dispersion liquid is prepared; on the other hand, active sites are provided for the loading of silver ions.

After obtaining the modified halloysite nanotube, the invention adds Na and the modified halloysite nanotube ₂HPO ₄·12H ₂Mixing O, ethylene glycol and dimethyl sulfoxide to obtain a solution B; in the invention, the modified halloysite nanotubes and Na ₂HPO ₄·12H ₂The mass ratio of O is preferably 2: (0.25 to 0.5), more preferably 2: (0.3 to 0.45), most preferably 2: (0.35-0.4); the preferable dosage ratio of the modified halloysite nanotube, the glycol and the dimethyl sulfoxide is 2: 1: (1-10), more preferably 2: 1: 6. the present invention does not limit the mixing in any particular way, and the mixing may be carried out by a process known to those skilled in the art.

Said HNTs-Ag ₃PO ₄The preparation method of the composite particle also comprises the steps of mixing silver nitrate solution, glycol and dimethyl sulfoxide to obtain solution A; in the invention, the concentration of the silver nitrate solution is preferably 0.3 mol/L; the volume ratio of the silver nitrate solution to the ethylene glycol to the dimethyl sulfoxide is preferably 1: (0.15-0.6): 1, more preferably 1: (0.2-0.25): 1; the mixing according to the present invention is not particularly limited, and may be carried out by a procedure known to those skilled in the art.

After the solution A and the solution B are obtained, the solution A and the solution B are mixed and loaded to obtain the HNTs-Ag ₃PO ₄Composite particles. In the invention, the volume ratio of the solution A to the solution B is preferably (3-10): 1, more preferably 9: 1. the present invention does not limit the mixing in any particular way, and the mixing may be carried out by a process known to those skilled in the art. In the present invention, the loading is preferably carried out under stirring conditions, the stirring time is preferably 4 hours, and the stirring rate is not particularly limited in the present invention and may be carried out at a rate well known to those skilled in the art.

After the loading is finished, the obtained product system is preferably subjected to centrifugation, washing, suction filtration, drying and grinding in sequence. In the invention, the rotation speed of the centrifugation is preferably 4000rpm, and the time of the centrifugation is preferably 5 min; the washing, suction filtration, drying and grinding are not limited in any way, and can be carried out by adopting the processes well known to the skilled person.

The invention is used for preparing the polyacrylonitrile solution and HNTs-Ag ₃PO ₄The mixing of the composite particles is not particularly limited, and may be carried out by a process well known to those skilled in the art.

After the spinning solution is obtained, the invention takes the non-woven fabric as the substrate, and carries out electrostatic spinning on the spinning solution to obtain the antibacterial composite nanofiber membrane. In the present invention, the nonwoven fabric is preferably a PET nonwoven fabric; the electrostatic spinning is preferably carried out by adopting a multi-spinneret spinning mode; the number of the spinnerets for spinning by the multi-spinneret is preferably 2-10, and more preferably 3; the electrostatic spinning process is preferably as follows: and respectively injecting the mixed spinning solution into a plurality of injectors, installing the injectors on a spinning machine, and adjusting the advancing speed of the spinning solution and the moving range of the injectors to carry out electrostatic spinning.

In the invention, the temperature of the electrostatic spinning is preferably 50-60 ℃, more preferably 52-58 ℃, and most preferably 54-56 ℃; the electrostatic voltage of the electrostatic spinning is preferably 15-22 kV, and more preferably 18 kV; the time of electrostatic spinning is preferably 1-5 h, and more preferably 4 h. The advancing speed of the spinning solution is preferably 0.8mL/h, and the spinning distance is preferably 15 cm.

The invention also provides the application of the antibacterial composite nanofiber membrane in the technical scheme or the antibacterial composite nanofiber membrane prepared by the preparation method in the technical scheme in the preparation of air purification materials. The method of application of the present invention is not particularly limited, and may be carried out by a method known to those skilled in the art.

The following examples are provided to illustrate the antibacterial composite nanofiber membrane of the present invention and the preparation method and application thereof in detail, but they should not be construed as limiting the scope of the present invention.