CN114351357B - Flexible bactericidal nanofiber membrane and preparation method and application thereof - Google Patents

Flexible bactericidal nanofiber membrane and preparation method and application thereof Download PDF

Info

Publication number
CN114351357B
CN114351357B CN202210029541.1A CN202210029541A CN114351357B CN 114351357 B CN114351357 B CN 114351357B CN 202210029541 A CN202210029541 A CN 202210029541A CN 114351357 B CN114351357 B CN 114351357B
Authority
CN
China
Prior art keywords
flexible
bactericidal
nanofiber membrane
temperature
nanofiber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210029541.1A
Other languages
Chinese (zh)
Other versions
CN114351357A (en
Inventor
张振翼
吕娜
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Minzu University
Original Assignee
Dalian Minzu University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian Minzu University filed Critical Dalian Minzu University
Priority to CN202210029541.1A priority Critical patent/CN114351357B/en
Publication of CN114351357A publication Critical patent/CN114351357A/en
Application granted granted Critical
Publication of CN114351357B publication Critical patent/CN114351357B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D13/00—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches
    • A41D13/05—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches protecting only a particular body part
    • A41D13/11—Protective face masks, e.g. for surgical use, or for use in foul atmospheres
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/103—Agents inhibiting growth of microorganisms
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
    • D06C7/00—Heating or cooling textile fabrics
    • D06C7/04—Carbonising or oxidising
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
    • F24F3/00—Air-conditioning systems in which conditioned primary air is supplied from one or more central stations to distributing units in the rooms or spaces where it may receive secondary treatment; Apparatus specially designed for such systems
    • F24F3/12—Air-conditioning systems in which conditioned primary air is supplied from one or more central stations to distributing units in the rooms or spaces where it may receive secondary treatment; Apparatus specially designed for such systems characterised by the treatment of the air otherwise than by heating and cooling
    • F24F3/16—Air-conditioning systems in which conditioned primary air is supplied from one or more central stations to distributing units in the rooms or spaces where it may receive secondary treatment; Apparatus specially designed for such systems characterised by the treatment of the air otherwise than by heating and cooling by purification, e.g. by filtering; by sterilisation; by ozonisation
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/13—Physical properties anti-allergenic or anti-bacterial

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Physical Education & Sports Medicine (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Combustion & Propulsion (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Catalysts (AREA)
  • Artificial Filaments (AREA)

Abstract

The invention provides a flexible bactericidal nanofiber membrane and a preparation method and application thereof, and belongs to the technical field of photocatalytic sterilization. The flexible bactericidal nanofiber membrane provided by the invention comprises a carbon nanofiber membrane matrix and Ag nanoparticles and TiO uniformly distributed in the carbon nanofiber membrane matrix 2 A nanoparticle; ag and TiO in the flexible bactericidal nanofiber membrane 2 The ratio of the amounts of substances of (a) to (b) is x: (100-x); wherein x =0.1 to 2. The flexible bactericidal nanofiber membrane provided by the invention is not prepared by mixing Ag nanoparticles and TiO 2 The nano-particles are loaded on the surface of the fiber, but Ag and TiO 2 The nano particles are uniformly distributed in the carbon nano fiber film matrix, so that the problem of falling off of the nano particles can not occur; the invention adds Ag and TiO into the carbon nano fiber film matrix at the same time 2 In light of Ag and TiO 2 Can be used for remarkably improving the bacteriostatic and bactericidal effects of the flexible bactericidal nanofiber membrane under the synergistic action.

Description

Flexible bactericidal nanofiber membrane and preparation method and application thereof
Technical Field
The invention relates to the technical field of photocatalytic sterilization, in particular to a flexible sterilization nanofiber membrane and a preparation method and application thereof.
Background
In the influenza season, in the haze weather, or in the places such as hospitals and theaters where people are dense, a large amount of harmful substances such as bacteria, epidemic viruses and small-sized Particulate Matters (PM) are bred in the air. At present, the prior art has limited means for protecting and treating the harmful substances, and the most common method is to adsorb and filter the harmful substances by a physical (mask interception and activated carbon adsorption) or chemical (chemical adsorption) method so as to achieve the aim of air purification. However, there are problems in terms of environmental protection, safety, and economy based on the air purification material used in the method: (1) The air purifying material can only play a role in filtering and adsorbing harmful substances and cannot eliminate or convert the harmful substances; (2) After the air purification material is saturated in adsorption, harmful substances can be released, so that secondary pollution is caused; and (3) the air purification material cannot be reused after adsorption. Based on the current situation statistics, the demands and consumption of the mask and the medical purification equipment are extremely high. Wherein, the average number of medical masks is at least 2 per person per day, and most of the medical masks are disposable products, which causes a great deal of resource waste. Therefore, designing and producing reusable self-cleaning masks and medical air purification materials is the current focus of research.
The traditional sterilization technology is generally high-temperature sterilization, high-pressure sterilization, radiation sterilization and the like, and although the sterilization technology is very effective, the traditional sterilization technology has large economic and energy consumption and is difficult to meet daily use. The photocatalytic sterilization technology is normal-temperature and normal-pressure sterilization, and brings a technical revolution to the traditional sterilization technology. Such as nano TiO 2 The particles can generate active groups with strong oxidizing property under the irradiation of ultraviolet light, and can effectively kill bacteria. But due to the nano TiO 2 The particles are small and are easily inhaled into the human body during respiration and the like, so that the particles are not suitable for direct use and a suitable carrier needs to be found. TiO prepared in the prior art 2 The composite with the fiber membrane is usually prepared by directly immersing the fiber membrane in a sol containing a titanium source for adsorption and then performing hydrothermal reaction, however, the composite obtained thereby is only TiO 2 Particles are loaded on the surface of a fiber membrane, for example, an invention patent with the application number of 201810555699.6 discloses a self-cleaning titanium dioxide nano-fiber membrane material, a preparation method and application thereof, the invention patent is that titanium dioxide nano-fibers are grown on the surface of carbon paper and self-assembled to form a membrane to obtain the titanium dioxide nano-fiber membrane material, but the titanium dioxide nano-fiber membrane material still causes TiO in the process of reusing the fiber membrane 2 The particles fall off, which not only affects the health of human body, but also reduces the photocatalytic sterilization performance of the composite material. Therefore, it is highly desirable to provide a flexible bactericidal nanofiber membrane that can ensure the presence of TiO 2 The particles can be effectively combined on the fiber membrane, and meanwhile, an excellent sterilization effect can be obtained, so that the daily use requirement of people can be better met.
Disclosure of Invention
The invention provides a flexible bactericidal nanofiber membrane and a preparation method and application thereof 2 The falling of the particles is more beneficial to maintainingIt can protect human health.
In order to achieve the above object, the present invention provides the following technical solutions:
the flexible bactericidal nanofiber membrane comprises a carbon nanofiber membrane matrix and Ag nanoparticles and TiO which are uniformly distributed in the carbon nanofiber membrane matrix 2 A nanoparticle; ag and TiO in the flexible bactericidal nanofiber membrane 2 The ratio of the amounts of substances of (b) is x: (100-x); wherein x =0.1 to 2.
Preferably, the average diameter of the carbon nanofibers in the carbon nanofiber membrane matrix is 300 to 600nm.
The invention also provides a preparation method of the flexible bactericidal nanofiber membrane in the technical scheme, which comprises the following steps:
(1) Mixing a carbon source, a silver source, a titanium source, acetic acid and a solvent to obtain precursor sol;
(2) Performing electrostatic spinning on the precursor sol obtained in the step (1) to obtain a flexible bactericidal nanofiber precursor;
(3) And (3) calcining the flexible bactericidal nanofiber precursor obtained in the step (2) to obtain the flexible bactericidal nanofiber membrane.
Preferably, the volume ratio of the titanium source, the acetic acid and the solvent in the step (1) is (1-4) mL: (8-12) mL.
Preferably, the amount ratio of the carbon source to the solvent in the step (1) is (1-1.3) g:10mL.
Preferably, the voltage of the electrostatic spinning in the step (2) is 8 to 20kV, the receiving distance of the electrostatic spinning is 10 to 20cm, and the diameter of the nozzle of the electrostatic spinning is 0.4 to 0.8mm.
Preferably, the calcining in step (3) comprises: heating to the first stage calcining temperature for heat preservation, and then continuing heating to the second stage calcining temperature for heat preservation; the temperature of the first stage of calcination is 200-290 ℃, and the heat preservation time at the temperature of the first stage of calcination is 0-240 min; the temperature of the second-stage calcination is 900-1100 ℃, and the heat preservation time at the temperature of the second-stage calcination is 0-120 min.
Preferably, the heating rate of heating to the first-stage calcining temperature is 0.5-2 ℃/min; the heating rate of the second section calcination temperature is 4-10 ℃/min.
Preferably, the atmosphere of the second stage calcination in the step (3) is nitrogen.
The invention also provides application of the flexible bactericidal nanofiber membrane in the technical scheme or the flexible bactericidal nanofiber membrane prepared by the preparation method in the technical scheme in an antibacterial mask or an air purifier.
The invention provides a flexible bactericidal nanofiber membrane which comprises a carbon nanofiber membrane matrix and Ag nanoparticles and TiO uniformly distributed in the carbon nanofiber membrane matrix 2 A nanoparticle; ag and TiO in the flexible bactericidal nanofiber membrane 2 The ratio of the amounts of substances of (b) is x: (100-x); wherein x =0.1 to 2. The invention is prepared by mixing Ag nanoparticles and TiO 2 The nano particles are distributed in the carbon nano fiber film matrix, so that Ag nano particles and TiO are uniformly distributed in the fiber tissue and on the fiber surface of the carbon nano fiber film matrix 2 Nanoparticles, and Ag nanoparticles and TiO on the fiber surface of the carbon nanofiber membrane substrate 2 The nano particles are not simply physically adsorbed on the surface of the fiber but uniformly distributed in the carbon nano fiber film matrix, so that the Ag nano particles and TiO nano particles can not occur 2 The problem of nanoparticle shedding; in addition, the invention adds Ag and TiO simultaneously 2 Under light, tiO 2 The Ag nano particles can capture electrons and the carbon nano fiber matrix with good conductivity can also transfer the electrons quickly, thereby reducing the recombination rate of photo-generated electron-hole pairs and promoting OH - And O 2- The generation of active oxygen (ROS) components can effectively lead to the rupture and death of bacteria; moreover, ag nanoparticles can also generate Reactive Oxygen Species (ROS) and produce Ag + Further exacerbating bacterial death. Therefore, the present invention combines Ag and TiO 2 The nano particles are uniformly dispersed in the carbon nano fiber with good conductivity, so that the synergistic effect of the nano particles can be realized, and the flexible bactericidal nano fiber membrane is obviously improvedThe photocatalysis antibacterial and bactericidal effect.
The results of the embodiment show that when the flexible bactericidal nanofiber membrane provided by the invention is used for an antibacterial mask, the bacteria liquid of escherichia coli is coated on the surface of the antibacterial mask, and the escherichia coli can be completely killed after the irradiation of simulated sunlight for 7 minutes; meanwhile, the flexible bactericidal nanofiber membrane provided by the invention has a bactericidal rate of over 98% on staphylococcus aureus and has a good bacteriostatic action on escherichia coli and staphylococcus aureus.
Drawings
Fig. 1 is an SEM image, a TEM image and corresponding elemental distribution diagram of a cross section of an individual fiber in a flexible bactericidal nanofiber membrane of example 1 of the present invention; wherein, FIG. 1 (A) is SEM picture of sample of example 1, FIG. 1 (B) is TEM picture of sample of example 1, FIG. 1 (C) is O element distribution diagram of sample of example 1, and FIG. 1 (D) is Ag element distribution diagram of sample of example 1; FIG. 1 (E) is a distribution diagram of Ti element of the sample of example 1; FIG. 1 (F) is a diagram showing the elemental distribution of sample C in example 1;
FIG. 2 is an X-ray diffraction pattern of the flexible bactericidal nanofiber membrane provided in example 1 of the present invention and comparative examples 1 to 2;
fig. 3 is a raman spectrum of the flexible bactericidal nanofiber membrane of example 1 of the present invention;
FIG. 4 is a graph showing the relationship between the sterilization rate of Escherichia coli in different illumination time for the flexible sterilization nanofiber membranes provided in example 1 of the present invention and in comparative examples 1 to 3; wherein (a) the curve is the relation curve of the sample of example 1, (b) the curve is the relation curve of the sample of comparative example 2, (c) the curve is the relation curve of the sample of comparative example 1, and (d) the curve is the relation curve of the sample of comparative example 3;
FIG. 5 is a graph showing the relationship between the sterilization rate of Staphylococcus aureus in the flexible sterilization nanofiber membrane of example 1 of the present invention under different illumination times;
fig. 6 is a bacteriostatic effect graph of the flexible bactericidal nanofiber membranes provided in example 1 and comparative examples 1 to 3 of the present invention under the irradiation without simulated sunlight.
Detailed Description
The invention provides a flexible bactericidal nanofiber membraneComprises a carbon nanofiber membrane matrix and Ag nano-particles and TiO which are uniformly distributed in the carbon nanofiber membrane matrix 2 A nanoparticle; ag and TiO in the flexible bactericidal nanofiber membrane 2 The ratio of the amounts of substances of (a) to (b) is x: (100-x); wherein x =0.1 to 2.
The flexible bactericidal nanofiber membrane provided by the invention comprises a carbon nanofiber membrane substrate. According to the invention, the carbon nanofiber membrane matrix is modified, so that the carbon nanofiber membrane has good flexibility and good sterilization performance, and can better meet the daily use requirements of people.
In the present invention, the average diameter of the carbon nanofibers in the carbon nanofiber membrane matrix is preferably 300 to 600nm, more preferably 310 to 550nm, and most preferably 320 to 500nm. The invention is more beneficial to the uniform distribution of modified nanoparticles by controlling the average diameter of the carbon nanofibers in the carbon nanofiber membrane matrix, and the carbon nanofiber membrane matrix keeps good flexibility.
The flexible bactericidal nanofiber membrane provided by the invention comprises Ag nanoparticles and TiO uniformly distributed in a carbon nanofiber membrane matrix 2 And (3) nanoparticles. The invention is prepared by mixing Ag nanoparticles and TiO 2 The nano particles are uniformly distributed in the carbon nano fiber membrane matrix, and effectively solves the problems of Ag nano particles and TiO 2 The nano particles are easy to fall off, and the Ag nano particles and TiO exposed on the surface of the carbon nano fiber film substrate 2 The nano particles can effectively perform photocatalytic reaction, and under the irradiation of light, tiO 2 The Ag nano particles can capture electrons and the carbon nano fiber matrix with good conductivity can also transfer the electrons quickly, thereby reducing the recombination rate of photo-generated electron-hole pairs and promoting OH - And O 2- The generation of active oxygen (ROS) components can effectively lead to the rupture and death of bacteria; and Ag nanoparticles can also generate Reactive Oxygen Species (ROS) components and produce Ag + Further aggravating bacterial death, i.e. Ag nanoparticles, tiO 2 The nano particles and the carbon nano fiber matrix can synergistically enhance the sterilization performance of the flexible sterilization nano fiber membrane.
In the present invention, the TiO is 2 The crystal structure of the nanoparticles is preferably a rutile structure. The invention controls TiO 2 The crystal structure of the nano-particles is rutile structure, so that TiO can be enabled to be 2 The photocatalysis performance of the nano particles is more stable, so that the nano particles have the effects of long-term bacteriostasis and antibiosis while efficiently sterilizing.
In the invention, ag and TiO in the flexible bactericidal nanofiber membrane 2 The ratio of the amounts of substances of (a) to (b) is x: (100-x); among them, x =0.1 to 2, preferably x =0.2 to 1.8, more preferably x =0.5 to 1.5, most preferably x =0.8 to 1.2, and further preferably x =1. The invention can control Ag and TiO in the flexible bactericidal nanofiber membrane 2 The ratio of the amount of the substance(s) is within the above range, which is more favorable for further improving the antibacterial and bactericidal effects of the flexible bactericidal nanofiber membrane.
The flexible bactericidal nanofiber membrane provided by the invention is prepared by mixing Ag nanoparticles and TiO 2 The nano particles are uniformly dispersed in the carbon nano fiber matrix, so that the dropping of the nano particles can be avoided while the sterilization effect is effectively exerted, and the maintenance of the human health is facilitated.
The invention also provides a preparation method of the flexible bactericidal nanofiber membrane, which comprises the following steps:
(1) Mixing a carbon source, a silver source, a titanium source, acetic acid and a solvent to obtain precursor sol;
(2) Performing electrostatic spinning on the precursor sol obtained in the step (1) to obtain a flexible bactericidal nanofiber precursor;
(3) And (3) calcining the flexible bactericidal nanofiber precursor obtained in the step (2) to obtain the flexible bactericidal nanofiber membrane.
According to the invention, a carbon source, a silver source, a titanium source, acetic acid and a solvent are mixed to obtain precursor sol.
In the present invention, the carbon source preferably includes polyvinylpyrrolidone. In the present invention, the molecular weight of the polyvinylpyrrolidone is preferably 90 ten thousand or more, and more preferably 130 ten thousand. The invention is more beneficial to the carbonization of the carbon source into the carbon nanofiber membrane with good flexibility by controlling the variety and the molecular weight of the carbon source in the range.
In the present invention, the silver source preferably includes one of silver nitrate, silver acetate and silver acetylacetonate, more preferably silver nitrate. The silver source is selected to be more beneficial to the uniform dispersion in the solvent, so that the silver source is uniformly dispersed in the carbon nano fiber matrix.
In the present invention, the titanium source preferably comprises butyl titanate. The titanium source is selected to be more beneficial to the uniform dispersion in the solvent, so that the titanium source is uniformly dispersed in the carbon nano fiber matrix.
In the present invention, the solvent preferably includes one or more of N, N-dimethylformamide, ethanol and chloroform, and more preferably ethanol. The invention is more beneficial to the uniform dispersion of each component by selecting the solvents of the types.
In the present invention, the volume ratio of the titanium source, acetic acid and solvent is preferably (1 to 4) mL: (8-12) mL, more preferably (2-3) mL, (2-3) mL: (9-11) mL. According to the invention, by controlling the volume ratio of the titanium source, the acetic acid and the solvent within the range, the hydrolysis of the titanium source is inhibited under the action of the acetic acid, and the titanium source is uniformly dispersed in the solvent.
In the present invention, the ratio of the amount of the carbon source to the amount of the solvent is preferably (1 to 1.3) g:10mL, more preferably (1.1 to 1.2) g:10mL. According to the invention, by controlling the dosage ratio of the carbon source and the solvent within the range, the carbon source is more favorably and uniformly dispersed into the solvent to form precursor sol with moderate viscosity, and the nanofiber precursor is favorably formed in the electrostatic spinning process, so that the carbon nanofibers with uniform diameters are fully carbonized.
In the present invention, the mixing is preferably performed under stirring conditions. The stirring rate and time are not particularly limited in the present invention, and the components can be uniformly mixed and formed into a sol system by using a stirring operation well known to those skilled in the art. In the present invention, the temperature of the mixing is preferably room temperature.
After the precursor sol is obtained, the precursor sol is subjected to electrostatic spinning to obtain the flexible bactericidal nanofiber precursor.
In the present invention, the voltage of the electrospinning is preferably 8 to 20kV, more preferably 10 to 18kV, and most preferably 12 to 15kV; the receiving distance of the electrostatic spinning is preferably 10-20 cm, more preferably 12-18 cm, and most preferably 14-16 cm; the nozzle diameter of the electrospinning is preferably 0.4 to 0.8mm, more preferably 0.4 to 0.6mm, and most preferably 0.4mm. The invention is more beneficial to obtaining the carbon nanofiber membrane with uniform and continuous diameter and good flexibility by controlling the voltage, the receiving distance and the nozzle diameter of the electrostatic spinning within the range.
And calcining the flexible bactericidal nanofiber precursor to obtain the flexible bactericidal nanofiber membrane.
In the present invention, the calcination preferably includes: and raising the temperature to the first stage calcining temperature for heat preservation, and then continuing raising the temperature to the second stage calcining temperature for heat preservation.
In the present invention, the temperature of the first stage calcination is preferably 200 to 290 ℃, more preferably 220 to 280 ℃, and most preferably 250 to 275 ℃; the time for holding at the temperature of the first stage calcination is preferably 0 to 240min, more preferably 10 to 200min, and most preferably 20 to 150min. According to the invention, the temperature and time of the first stage of calcination are controlled within the above range, so that the flexible sterilization nanofiber precursor can be fully pre-oxidized, and the shape of the flexible sterilization nanofiber precursor is stabilized, thereby being more beneficial to obtaining a flexible sterilization nanofiber membrane with uniform and continuous diameter.
In the present invention, the rate of temperature rise to the first-stage calcination temperature is preferably 0.5 to 2 ℃/min, more preferably 0.8 to 1.5 ℃/min, and most preferably 1 to 1.2 ℃/min. According to the invention, the heating rate of the first-stage calcining temperature is controlled within the range, so that the flexible sterilization nanofiber precursor can be fully pre-oxidized.
In the present invention, the temperature of the second stage calcination is preferably 900 to 1100 ℃, more preferably 950 to 1050 ℃, and most preferably 1000 ℃; the time for holding at the temperature of the second stage calcination is preferably 0 to 120min, more preferablyPreferably 10 to 100min, most preferably 20 to 60min. The invention can fully carbonize the carbon source in the precursor by controlling the temperature and the time of the second stage of calcination within the range, form the carbon nanofiber matrix with good conductivity, and simultaneously ensure that the Ag nanoparticles and the TiO 2 The nano particles are synthesized in situ in the carbon nano fiber matrix and are uniformly distributed.
In the present invention, the rate of temperature increase to the second-stage calcination temperature is 4 to 10 ℃/min, preferably 4.5 to 8 ℃/min, and more preferably 5 to 6 ℃/min. The invention is more beneficial to forming Ag nano particles and TiO with smaller size in the carbonization process by controlling the temperature rise rate of the second section calcination temperature to be in the range 2 The nano particles are used for obtaining the flexible bactericidal nano fiber film with good flexibility and uniformly distributed nano particles.
In the present invention, the atmosphere of the second stage calcination is preferably nitrogen. According to the invention, the atmosphere of the second-stage calcination is controlled to be nitrogen, so that the oxidation of carbonized carbon nano-fibers and silver nano-particles can be avoided, and the flexible bactericidal nano-fiber membrane with good antibacterial and bactericidal performances can be obtained.
In the present invention, the cooling method after the second stage calcination is preferably natural cooling to room temperature.
The preparation method provided by the invention combines Ag nano-particles and TiO 2 The nano particles are synthesized in situ in the carbon nano fiber matrix, and are in a uniformly dispersed state, so that the nano particles can be prevented from falling off while the sterilization effect is exerted efficiently; the preparation method disclosed by the invention is simple in process, easy to control parameters, low in cost, green and environment-friendly, and more suitable for large-scale production.
The invention also provides application of the flexible bactericidal nanofiber membrane in the technical scheme or the flexible bactericidal nanofiber membrane prepared by the preparation method in the technical scheme in an antibacterial mask or an air purifier.
In the present invention, the air purifier preferably includes a PM2.5 filter or a medical air purifier.
The flexible bactericidal nanofiber membrane provided by the invention can be used for daily use of people and also can be used for medical air purification, and can effectively kill common bacteria such as escherichia coli and staphylococcus aureus under the irradiation of natural light or ultraviolet light and resist the propagation of the bacteria for a long time, so that the flexible bactericidal nanofiber membrane is more beneficial to the maintenance of human health.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Example 1
The embodiment provides a flexible bactericidal nanofiber membrane which comprises a carbon nanofiber membrane matrix and Ag nanoparticles and TiO uniformly distributed in the carbon nanofiber membrane matrix 2 Nanoparticle (rutile structure) composition; ag and TiO in flexible bactericidal nanofiber membrane 2 The ratio of the amounts of substances of (a) to (b) is x: (100-x); wherein x =1.
Ag/TiO 2 The average diameter of a single nanofiber in the carbon nanofiber membrane is 350nm;
the preparation method of the flexible bactericidal nanofiber membrane specifically comprises the following steps:
(1) Mixing a carbon source (1.1 g of polyvinylpyrrolidone, the molecular weight of 130 ten thousand), a silver source (15 mg of silver nitrate), a titanium source (3 mL of butyl titanate), acetic acid (3 mL) and a solvent (10 mL of ethanol) to obtain precursor sol; wherein the mixing is stirring, and the mixing temperature is room temperature.
(2) Performing electrostatic spinning on the precursor sol obtained in the step (1) to obtain a flexible bactericidal nanofiber precursor; the electrostatic spinning process specifically comprises the following steps: putting the precursor sol into a medical injector with a nozzle with the diameter of 0.4mm, keeping the distance between the nozzle and a grounding receiving plate to be 15cm, putting a gold electrode into the solution, applying high voltage of 15kV, and performing electrostatic spinning to prepare a flexible bactericidal nanofiber precursor;
(3) Calcining the flexible bactericidal nanofiber precursor obtained in the step (2) to obtain a flexible bactericidal nanofiber membrane; wherein, the calcining process specifically comprises the following steps: and (3) placing the flexible bactericidal nanofiber precursor in a tubular furnace, heating to the first-stage calcination temperature of 270 ℃ at the speed of 1 ℃/min, then heating to the second-stage calcination temperature of 1000 ℃ at the speed of 5 ℃/min under the protection of nitrogen, and naturally cooling to room temperature to obtain the flexible bactericidal nanofiber membrane.
Comparative example 1
The Ag nano particles in the product of the example 1 and the silver source in the preparation method are omitted, and the carbon nano fiber matrix only containing TiO is prepared under the same conditions of other parameters as the example 1 2 Flexible bactericidal nanofiber membranes of nanoparticles.
Comparative example 2
Omitting TiO from the product of example 1 2 The flexible bactericidal nanofiber membrane containing only Ag nanoparticles in the carbon nanofiber matrix was prepared under the same conditions as the other parameters of example 1 by adding the nanoparticles and the titanium source in the preparation method.
Comparative example 3
Interlayer of common commercial mask, no Ag and no TiO 2 The fibrous membrane material of (1).
1. Material characterization
The cross section of a single fiber in the flexible bactericidal nanofiber membrane provided in example 1 is observed under a scanning electron microscope and a transmission electron microscope, and a corresponding element distribution photograph is tested and shown in fig. 1; wherein, FIG. 1 (A) is SEM picture of sample of example 1, FIG. 1 (B) is TEM picture of sample of example 1, FIG. 1 (C) is O element distribution diagram of sample of example 1, and FIG. 1 (D) is Ag element distribution diagram of sample of example 1; FIG. 1 (E) is a distribution diagram of Ti element of the sample of example 1; FIG. 1 (F) is a chart of elemental distribution of sample C in example 1.
As clearly seen from fig. 1 (a), the diameter of the individual fibers in the prepared flexible bactericidal nanofiber membrane is about 350nm; meanwhile, as can be seen from the element distribution diagrams of the cross sections of the fibers in FIGS. 1 (C) to (F), ag nanoparticles and TiO are uniformly distributed in and on the fiber 2 The nanoparticles are not distributed only on the surface of the fibers. Therefore, the Ag nano in the flexible bactericidal nanofiber membrane provided by the invention is proved to beParticles and TiO 2 The nano particles are uniformly dispersed in the carbon fiber and on the surface of the carbon fiber, so that the falling of the nano particles can be avoided.
The flexible bactericidal nanofiber membranes provided in example 1 and comparative examples 1 to 2 were subjected to X-ray diffraction pattern analysis, and the results are shown in fig. 2.
As can be seen from FIG. 2, the Ag/TiO provided in example 1 2 The X-ray diffraction pattern of the carbon nanofiber membrane simultaneously shows rutile structure TiO 2 The characteristic diffraction peak of the nanocrystalline and the characteristic diffraction peak of Ag prove that the Ag/TiO is successfully prepared 2 a/C nanofiber membrane. Similarly, comparative examples 1 and 2 provide TiO 2 Rutile TiO structure respectively appears in X-ray diffraction patterns of/carbon nanofiber membrane and Ag/carbon nanofiber membrane 2 The characteristic diffraction peak of the nano crystal and the characteristic diffraction peak of Ag prove that the TiO is successfully prepared 2 a/C nanofiber membrane and an Ag/C nanofiber membrane.
Raman spectrum analysis was performed on the flexible bactericidal nanofiber membrane provided in example 1, and the result is shown in fig. 3.
As can be seen from FIG. 3, at 1350cm -1 And 1580cm -1 Clear D peak and G peak appear respectively, and I D /I G 0.965, demonstrating that a carbon nanofiber membrane matrix with a high degree of graphitization can be formed under high temperature calcination conditions of 1000 ℃.
2. Test of bactericidal and antibacterial properties
The flexible sterilization nanofiber membranes provided in the embodiment 1 and the comparative examples 1 to 3 are respectively cut into membranes with uniform sizes of 1cm × 1.5cm, 50 μ L of diluted escherichia coli bacterial liquid is respectively coated on the membranes with the sizes of 1cm × 1.5cm, irradiation is carried out under a xenon lamp provided with a simulated sunlight filter, sampling is carried out at 3min, 5min, 7min and 10min respectively, the membranes are placed into a test tube provided with 10mL of sterile water, shaking is carried out uniformly, 50 μ L of bacterial liquid is taken for plating, and the test tube is placed in a 37 ℃ incubator for culturing for 24 hours.
FIG. 4 is a graph showing the relationship between the E.coli sterilization rate of the flexible sterilization nanofiber membranes provided in example 1 and comparative examples 1-3 in different illumination time, wherein (a) the graph is the graph showing the relationship between the samples in example 1, (b) the graph is the graph showing the relationship between the samples in comparative example 2, (c) the graph is the graph showing the relationship between the samples in comparative example 1, and (d) the graph is the graph showing the relationship between the samples in comparative example 3.
As can be seen from fig. 4, the escherichia coli concentration on the surface of the flexible bactericidal nanofiber membrane provided in example 1 is already close to 0 at 3min, which is significantly lower than that in comparative examples 1 to 3, and it is proved that the flexible bactericidal nanofiber membrane provided in the invention has better photocatalytic bactericidal activity.
Fig. 5 is a graph showing the relationship between the sterilization rate of staphylococcus aureus in the flexible sterilization nanofiber membrane of example 1 of the present invention under different illumination times. As can be seen from FIG. 5, the sterilization rate of the flexible sterilization nanofiber membrane provided by the invention on staphylococcus aureus can reach more than 98%.
Coli and staphylococcus aureus were plated, respectively, and each 1cm × 1.5cm fiber membrane was placed in a medium, and the bacteriostatic effect was tested without simulated solar irradiation, as in the above-described plating and culturing methods of e.
Fig. 6 is a bacteriostatic effect graph of the flexible bactericidal nanofiber membranes provided in example 1 and comparative examples 1 to 3 under the condition of no simulated sunlight irradiation.
As can be clearly seen from fig. 6, under the condition of no irradiation of simulated sunlight, the fiber membranes provided in example 1 and comparative example 2 can still have obvious inhibition zones under the condition of no irradiation of simulated sunlight, while the fiber membranes provided in comparative example 1 and comparative example 3 do not have inhibition zones; in addition, the inhibition zone of the comparative example 2 is obviously smaller than that of the example 1, and the flexible bactericidal nanofiber membrane provided by the invention is proved to have a good inhibition effect.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.

Claims (7)

1. A flexible antibacterial nanofiber membrane comprises a carbon nanofiber membrane matrix and a flexible antibacterial nanofiber membrane uniformly distributed on the matrixAg nanoparticles and TiO in the carbon nanofiber membrane matrix 2 A nanoparticle; ag and TiO in the flexible bactericidal nanofiber membrane 2 The ratio of the amounts of substances of (a) to (b) is x: (100-x); wherein x = 0.8-1.2;
the preparation method of the flexible bactericidal nanofiber membrane comprises the following steps:
(1) Mixing a carbon source, a silver source, a titanium source, acetic acid and a solvent to obtain precursor sol;
(2) Performing electrostatic spinning on the precursor sol obtained in the step (1) to obtain a flexible bactericidal nanofiber precursor;
(3) Calcining the flexible bactericidal nanofiber precursor obtained in the step (2) to obtain a flexible bactericidal nanofiber membrane;
the calcination in the step (3) comprises: heating to the first section calcining temperature for heat preservation, and then continuing heating to the second section calcining temperature for heat preservation; the temperature of the first stage of calcination is 200-290 ℃, and the heat preservation time at the temperature of the first stage of calcination is 0-240 min; the temperature of the second-stage calcination is 900-1100 ℃, and the heat preservation time at the temperature of the second-stage calcination is 0-120 min;
the heating rate of heating to the first section calcining temperature is 0.5-2 ℃/min; the heating rate of heating to the second section calcining temperature is 4-10 ℃/min;
and (3) the atmosphere of the second-stage calcination is nitrogen.
2. The flexible antiseptic nanofiber membrane of claim 1, wherein the average diameter of the carbon nanofibers in the carbon nanofiber membrane matrix is 300-600 nm.
3. A method for preparing the flexible bactericidal nanofiber membrane as claimed in claim 1 or 2, comprising the steps of:
(1) Mixing a carbon source, a silver source, a titanium source, acetic acid and a solvent to obtain precursor sol;
(2) Performing electrostatic spinning on the precursor sol obtained in the step (1) to obtain a flexible bactericidal nanofiber precursor;
(3) Calcining the flexible bactericidal nanofiber precursor obtained in the step (2) to obtain a flexible bactericidal nanofiber membrane;
the calcination in the step (3) comprises: heating to the first stage calcining temperature for heat preservation, and then continuing heating to the second stage calcining temperature for heat preservation; the temperature of the first stage of calcination is 200-290 ℃, and the heat preservation time at the temperature of the first stage of calcination is 0-240 min; the temperature of the second-stage calcination is 900-1100 ℃, and the heat preservation time at the temperature of the second-stage calcination is 0-120 min;
the heating rate of heating to the first section calcining temperature is 0.5-2 ℃/min; the heating rate of heating to the second section calcining temperature is 4-10 ℃/min;
and (3) the atmosphere of the second-stage calcination is nitrogen.
4. The preparation method according to claim 3, wherein the volume ratio of the titanium source, the acetic acid and the solvent in the step (1) is (1-4) mL: (8-12) mL.
5. The method according to claim 3, wherein the ratio of the amount of the carbon source to the amount of the solvent in the step (1) is (1 to 1.3) g:10mL.
6. The production method according to claim 3, wherein the voltage of the electrospinning in the step (2) is 8 to 20kV, the receiving distance of the electrospinning is 10 to 20cm, and the diameter of the nozzle of the electrospinning is 0.4 to 0.8mm.
7. The use of the flexible bactericidal nanofiber membrane as defined in any one of claims 1 to 2 or the flexible bactericidal nanofiber membrane prepared by the preparation method as defined in any one of claims 3 to 6 in an antibacterial mask or an air purifier.
CN202210029541.1A 2022-01-12 2022-01-12 Flexible bactericidal nanofiber membrane and preparation method and application thereof Active CN114351357B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210029541.1A CN114351357B (en) 2022-01-12 2022-01-12 Flexible bactericidal nanofiber membrane and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210029541.1A CN114351357B (en) 2022-01-12 2022-01-12 Flexible bactericidal nanofiber membrane and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114351357A CN114351357A (en) 2022-04-15
CN114351357B true CN114351357B (en) 2023-03-24

Family

ID=81109730

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210029541.1A Active CN114351357B (en) 2022-01-12 2022-01-12 Flexible bactericidal nanofiber membrane and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114351357B (en)

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8414806B2 (en) * 2008-03-28 2013-04-09 Nanyang Technological University Membrane made of a nanostructured material
CN105603714B (en) * 2016-01-23 2019-01-04 武汉理工大学 A kind of preparation method of titania-based silver-magnesia-dioxide composite nanofiber felt
CN105964249A (en) * 2016-05-18 2016-09-28 武汉汉缘和环保科技有限公司 Ag-TiO2 nano fiber as well as preparation and application thereof
US20180080148A1 (en) * 2016-09-16 2018-03-22 Paul K. Westerhoff Electrospun polymeric porous fibers containing nanomaterials
CN107051232B (en) * 2017-05-26 2020-06-16 山东知道知识产权运营有限公司 Sterilization and aldehyde removal air filtering membrane
CN107261865A (en) * 2017-06-25 2017-10-20 长沙善道新材料科技有限公司 A kind of functional form air filting material
CN109675450B (en) * 2018-12-26 2020-09-25 中国科学院深圳先进技术研究院 Antibacterial composite nanofiber membrane and preparation method and application thereof
CN111180727A (en) * 2020-02-17 2020-05-19 五邑大学 Preparation method and application of flexible compact carbon nanofiber membrane
CN113201858A (en) * 2021-05-08 2021-08-03 东华大学 Preparation method of flexible ultrafine porous carbon nanofiber-loaded oxide quantum dots

Also Published As

Publication number Publication date
CN114351357A (en) 2022-04-15

Similar Documents

Publication Publication Date Title
Tekin et al. Thermal, photocatalytic, and antibacterial properties of calcinated nano-TiO2/polymer composites
CN103015166B (en) Nano-silver antibacterial fabric and preparation method thereof
KR100811205B1 (en) Antibacterial nano-fibers containing silver nano-particles and preparation method thereof
CN101041134B (en) Modification bamboo charcoal having Ag and porous TiO2 and the preparing method
CN104722297A (en) Nano air purifying catalytic agent and preparation method thereof
CN106577750A (en) Preparing method for titanium-dioxide composite nanometer antibacterial material and product thereof
CN103843822A (en) Preparation method of silver composite antibacterial material of carbon nano tube
CN111418608A (en) Ag-MoS2@TiO2Nano photocatalytic bactericidal material and preparation method thereof
CN110038451A (en) Ceramic nanofibers base compound purifying film and its preparation method and application
CN111466655A (en) Photocatalyst mask and preparation method and application thereof
CN114351357B (en) Flexible bactericidal nanofiber membrane and preparation method and application thereof
Ruiz-Ramírez et al. Photocatalytic degradation of oxytetracycline by SiO2–TiO2–Ag electrospun fibers
CN110038452A (en) Load the ceramic nanofibers base compound purifying film and its preparation method and application of silver
CN103537197B (en) Preparation method of gas purification membrane with antibacterial function
Sabura et al. Monodispersed nanorod-shaped Mn-Co co-doped ZnO nanoparticles for enhanced photocatalytic and antibacterial activities
CN108002481A (en) A kind of water treating module
Qi et al. Improved photocatalytic and sterilization performance of Cu doped sea urchin-like WO 3− x
CN109621932A (en) White carbon black-titanic oxide composite photochemical catalyst antibacterial agent preparation method
CN114653355A (en) Photocatalytic material, preparation method and photocatalytic air epidemic prevention filter screen
CN114028954A (en) Preparation method and application of PAN @ aminated defect indium-based metal organic framework composite nanofiber membrane
CN106665695A (en) Antibacterial titanium dioxide composite micro-nano particle and preparation method thereof
Farah et al. Synthesis of CuO-TiO2 nano-composite for Escherichia coli disinfection and toluene degradation
Shahryari et al. A New Ultrasonic-Assisted Electrospun Method for Highly Efficient Synthesis of Co-Mof/Pva Polymeric Network: A Controllable Procedure for Navicula Algae Removal from Drinking Water
CN114657703B (en) TiO (titanium dioxide) 2 Ethylene urea/polyacrylonitrile formaldehyde-removing nanofiber membrane and preparation method and application thereof
CN111266108B (en) Preparation method of heterostructure nano photocatalytic coating and file cabinet

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant