CN116575144B - Preparation method for preparing antibacterial graphene fibers through electrostatic spinning - Google Patents
Preparation method for preparing antibacterial graphene fibers through electrostatic spinning Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 117
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 49
- 238000010041 electrostatic spinning Methods 0.000 title claims abstract description 26
- 239000000835 fiber Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920002301 cellulose acetate Polymers 0.000 claims abstract description 50
- 229910052582 BN Inorganic materials 0.000 claims abstract description 21
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004814 polyurethane Substances 0.000 claims abstract description 16
- 239000002105 nanoparticle Substances 0.000 claims abstract description 11
- 229920002635 polyurethane Polymers 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 57
- 229920000728 polyester Polymers 0.000 claims description 25
- 239000000017 hydrogel Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 20
- 239000002121 nanofiber Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000004964 aerogel Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- 229960005070 ascorbic acid Drugs 0.000 claims description 6
- 235000010323 ascorbic acid Nutrition 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 238000011282 treatment Methods 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 5
- 230000008014 freezing Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000009987 spinning Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000001523 electrospinning Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 52
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 26
- 241000894006 Bacteria Species 0.000 abstract description 9
- 230000001580 bacterial effect Effects 0.000 abstract description 7
- 238000005520 cutting process Methods 0.000 abstract description 6
- 230000004060 metabolic process Effects 0.000 abstract description 6
- 230000000241 respiratory effect Effects 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- 230000003385 bacteriostatic effect Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 30
- 230000000694 effects Effects 0.000 description 7
- 238000001000 micrograph Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 241000588724 Escherichia coli Species 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- 241000191967 Staphylococcus aureus Species 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000002054 inoculum Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
-
- 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
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- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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Abstract
The invention discloses a preparation method for preparing antibacterial graphene fibers through electrostatic spinning. According to the invention, graphene oxide is treated at a high temperature to obtain three-dimensional nitrogen doped graphene, and the three-dimensional nitrogen doped graphene and boron nitride are used as inorganic nano particles to be added into cellulose acetate/polyurethane solution, and the antibacterial graphene fiber is prepared through electrostatic spinning. The three-dimensional nitrogen doped graphene has high porosity and high specific surface area, and compared with graphene with a two-dimensional structure, the three-dimensional nitrogen doped graphene has more stable structure and better adsorption capacity, improves the cutting efficiency of bacteria, and realizes high antibacterial effect; meanwhile, the nitrogen doped graphene optimizes the electronic structure of the graphene, can efficiently capture electrons generated during bacterial respiratory metabolism, and improves the intrinsic bacteriostatic ability of the graphene. In addition, the cellulose acetate and the boron nitride also have certain antibacterial effect, and the nitrogen doped graphene, the cellulose acetate and the boron nitride play a synergistic effect, so that the antibacterial capability of the graphene fiber is improved together.
Description
Technical Field
The invention belongs to the field of graphene preparation, and particularly relates to a preparation method for preparing antibacterial graphene fibers through electrostatic spinning.
Background
Graphene is the thinnest known two-dimensional material, consisting of carbon atoms in sp 2 A cellular planar film formed by hybridization. The thickness of the monolayer graphene film is similar to that of the monolayer carbon atoms, and is about 0.335mm. The graphene has good electric conduction, heat conduction, light transmission, antibacterial, stretching resistance, radiation protection and other performances due to the unique structure, so that the graphene has wide application prospects in the aspects of photoelectricity, energy sources, medicine and health, functional fabrics and the like. The preparation of nontoxic, stable, efficient and broad-spectrum antibacterial composite fibers has become a focus of attention, and graphene also has important scientific value and great application prospect in the field of antibacterial fibers.
Based on the problems in the background art, the invention aims to provide a preparation method for preparing antibacterial graphene fibers through electrostatic spinning. The graphene oxide is treated at a high temperature to obtain three-dimensional nitrogen doped graphene, and the three-dimensional nitrogen doped graphene and boron nitride are added into cellulose acetate/polyurethane solution as inorganic nano particles, and the antibacterial graphene fiber is prepared through electrostatic spinning. The three-dimensional nitrogen doped graphene has high porosity and high specific surface area, and compared with graphene with a two-dimensional structure, the three-dimensional nitrogen doped graphene has a more stable structure and better adsorption capacity, improves the cutting efficiency of bacteria, and realizes a good sterilization effect; meanwhile, the nitrogen doped graphene optimizes the electronic structure of the graphene, can efficiently capture electrons generated during bacterial respiratory metabolism, and improves the intrinsic bacteriostatic ability of the graphene. In addition, the cellulose acetate and the boron nitride also have certain antibacterial effect, and the nitrogen doped graphene, the cellulose acetate and the boron nitride play a synergistic effect, so that the antibacterial capability of the graphene fiber is improved together.
Disclosure of Invention
In order to solve the defects in the prior art, the three-dimensional nitrogen-doped graphene is obtained by treating graphene oxide at a high temperature, and is added into cellulose acetate/polyurethane solution together with boron nitride as inorganic nano particles, so that the antibacterial graphene fiber is prepared through electrostatic spinning. The three-dimensional nitrogen doped graphene has high porosity and high specific surface area, and compared with graphene with a two-dimensional structure, the three-dimensional nitrogen doped graphene has a more stable structure and better adsorption capacity, improves the cutting efficiency of bacteria, and realizes a good sterilization effect; meanwhile, the nitrogen doped graphene optimizes the electronic structure of the graphene, can efficiently capture electrons generated during bacterial respiratory metabolism, and improves the intrinsic bacteriostatic ability of the graphene. In addition, the cellulose acetate and the boron nitride also have certain antibacterial effect, and the nitrogen doped graphene, the cellulose acetate and the boron nitride play a synergistic effect, so that the antibacterial capability of the graphene fiber is improved together.
In order to achieve the above purpose, the invention provides a method for preparing low-defect nanoscale graphene by a physical method, which comprises the following specific preparation steps:
s1, firstly, ultrasonically dispersing Graphene Oxide (GO) powder with a certain mass into 100ml of deionized water to finally obtain 2-5mg/ml of GO solution, mixing the GO solution with 20ml of ascorbic acid solution with the concentration of 50-150mg/ml, stirring by using a magnetic stirrer, pouring the solution into a customized glass mold when the solution is full of bubbles and the color turns from black to yellow, placing the glass mold into a baking oven at 60 ℃, standing, adding deionized water into the mold after hydrogel is formed, and then continuously standing for 10 hours to obtain partially reduced GO hydrogel;
s2, putting the GO hydrogel obtained in the step S1 into a refrigerator at the temperature of minus 60-80 ℃, fully freezing, taking out, compressing the hydrogel thawed at room temperature to 1cm by using a tablet press, putting into a muffle furnace, adding urea with a certain mass, heating to 150-350 ℃ at a certain speed, stopping, preserving heat for 2-6h, and naturally cooling to finally obtain the three-dimensional graphene (3 DNG) aerogel;
s3, taking 10mg of 3D NG aerogel in 50ml of distilled water, placing the suspension on a magnetic stirrer for stirring for 24 hours after ultrasonic treatment for 1 hour, filtering the solution, and carrying out freeze-drying treatment on filter residues by using a vacuum freeze dryer to finally obtain 3D NG with better dispersibility;
s4, firstly weighing a certain mass of Cellulose Acetate (CA), dissolving the cellulose acetate in an N, N-dimethylacetamide/acetone mixed solution with the mass ratio of 1:2 to obtain a CA solution with the concentration of 10-30wt%, then adding Polyurethane (PU) with the mass equal to that of the cellulose acetate into the solution, adding 3D NG and boron nitride inorganic nano particles into the PU/CA mixed solution with the mass ratio of 0.1-0.5:100, uniformly stirring the prepared solution for 24 hours at room temperature, then carrying out ultrasonic treatment in an ultrasonic cleaner for 30 minutes, continuing stirring for 1 hour, and repeating the steps for three times;
and S5, connecting a high-voltage power supply between the polyester net and the electrostatic spinning, ejecting the solution obtained in the step S4 from the tip of the capillary by using electrostatic spinning equipment to form graphene nanofibers, uniformly depositing the graphene nanofibers on the polyester net, gathering the polyester net into strips by using a bell mouth, and adding certain twist. Finally, preparing the graphene nanofiber blended yarn through a subsequent yarn forming process. The spinning voltage is 18kV, the receiving distance is 15cm, the push injection speed is 0.08mm/min, the thickness of the polyester net is 2mm, the breadth is 20cm, and the conveying speed of the polyester net is 140cm/min.
Preferably, the urea is added in an amount of 5mg in step S2.
The invention has the technical effects and advantages that:
1. the three-dimensional nitrogen doped graphene has high porosity and high specific surface area, and compared with the graphene with a two-dimensional structure, the three-dimensional nitrogen doped graphene has the advantages of being more stable in structure, better in adsorption capacity, improving the cutting efficiency of bacteria and achieving a good sterilization effect.
2. The nitrogen doped graphene optimizes the electronic structure of the graphene, can efficiently capture electrons generated during bacterial respiratory metabolism, and improves the intrinsic bacteriostatic ability of the graphene.
3. The cellulose acetate and the boron nitride also have certain antibacterial effect, and the nitrogen doped graphene, the cellulose acetate and the boron nitride play a synergistic effect, so that the antibacterial capability of the graphene fiber is improved together.
Drawings
Fig. 1 is a scanning electron microscope image of graphene prepared in example 1 of the present invention.
Fig. 2 is a scanning electron microscope image of the graphene prepared in comparative example 1 of the present invention.
Fig. 3 is a transmission electron microscope image of graphene prepared in example 2 of the present invention.
Fig. 4 is a transmission electron microscope image of the graphene prepared in comparative example 2 of the present invention.
Fig. 5 is a transmission electron microscope image of the graphene prepared in comparative example 3 of the present invention.
Fig. 6 is a raman spectrum of the prepared graphene of example 2, comparative example 2 and comparative example 3 of the present invention.
Fig. 7 is a graph showing the antibacterial ratio of the graphene nanofiber blended yarn prepared in example 3 and comparative examples 1, 2, 4 and 5 according to the present invention to staphylococcus aureus and escherichia coli.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
S1, firstly, ultrasonically dispersing Graphene Oxide (GO) powder with a certain mass into 100ml of deionized water to finally obtain 2mg/ml of GO solution, mixing the solution with 20ml of ascorbic acid solution with the concentration of 50mg/ml, stirring the mixture by using a magnetic stirrer, setting the parameters to 2500r/min for 5min, pouring the solution into a customized glass mold when the solution is full of bubbles and the color turns from black to yellow, placing the glass mold into a baking oven at 60 ℃, standing the glass mold, adding deionized water into the mold after hydrogel is formed, and then continuously standing for 10h to obtain partially reduced GO hydrogel;
s2, placing the GO hydrogel obtained in the step S1 into a refrigerator at minus 60 ℃, taking out the hydrogel after full freezing, compressing the hydrogel thawed at room temperature to 1cm by using a tablet press, placing the hydrogel into a muffle furnace, adding 5mg of urea, stopping heating to 150 ℃ at 2 ℃/min, preserving heat for 2 hours, and naturally cooling to finally obtain the three-dimensional graphene (3D NG) aerogel;
s3, taking 10mg of 3D NG aerogel in 50ml of distilled water, placing the suspension on a magnetic stirrer for stirring for 24 hours after ultrasonic treatment for 1 hour, filtering the solution, and carrying out freeze-drying treatment on filter residues by using a vacuum freeze dryer to finally obtain 3D NG with better dispersibility;
s4, weighing a certain mass of Cellulose Acetate (CA), dissolving the Cellulose Acetate (CA) in an N, N-dimethylacetamide/acetone mixed solution with a mass ratio of 1:2 to obtain a CA solution with a concentration of 10wt%, then adding Polyurethane (PU) with the same mass as that of the cellulose acetate into the solution, and mixing 3D NG and boron nitride inorganic nano particles according to a mass ratio of 1.2: adding the mass ratio of 0.5 into the PU/CA mixed solution to ensure that the mass ratio of the inorganic nano particles to the total mass of the PU/CA is 0.1:100, uniformly stirring the prepared solution for 24 hours at room temperature, then carrying out ultrasonic treatment in an ultrasonic cleaner for 30 minutes, continuing stirring for 1 hour, and repeating the steps for three times;
and S5, connecting a high-voltage power supply between the polyester net and the electrostatic spinning, ejecting the solution obtained in the step S4 from the tip of the capillary by using electrostatic spinning equipment to form graphene nanofibers, uniformly depositing the graphene nanofibers on the polyester net, gathering the polyester net into strips by using a bell mouth, and adding certain twist. Finally, preparing the graphene nanofiber blended yarn through a subsequent yarn forming process. The spinning voltage is 18kV, the receiving distance is 15cm, the push injection speed is 0.08mm/min, the thickness of the polyester net is 2mm, the breadth is 20cm, and the conveying speed of the polyester net is 140cm/min.
Comparative example 1
The procedure of example 1 was followed except that step S2 was omitted.
Fig. 1 and 2 are scanning electron microscope images of graphene prepared in example 1 and comparative example 1, respectively, of the present invention. From the scan, compared with comparative example 1, the graphene prepared in example 1 has higher porosity and high specific surface area, and the pore diameter varies from a few nanometers to tens of micrometers, which indicates that the graphene prepared by calcining has a better three-dimensional structure, and the structure has a promotion effect on improving the adsorption capacity of materials, further improving the cutting efficiency of bacteria and realizing a high antibacterial effect.
Example 2
S1, firstly, ultrasonically dispersing Graphene Oxide (GO) powder with a certain mass into 100ml of deionized water to finally obtain a GO solution with a concentration of 3mg/ml, mixing the GO solution with 20ml of ascorbic acid solution with a concentration of 100mg/ml, stirring by using a magnetic stirrer, pouring the solution into a customized glass mold when the solution is full of bubbles and the color turns from black to yellow, placing the glass mold into a baking oven with the temperature of 60 ℃, standing, adding deionized water into the mold after hydrogel is formed, and then continuously standing for 10 hours to obtain partially reduced GO hydrogel;
s2, putting the GO hydrogel obtained in the step S1 into a refrigerator at the temperature of minus 60-80 ℃, fully freezing, taking out, compressing the hydrogel thawed at room temperature to 1cm by using a tablet press, putting into a muffle furnace, adding 5mg of urea, stopping heating to 150-350 ℃ at the speed of 5 ℃/min, preserving heat for 2-6h, and naturally cooling to finally obtain the three-dimensional graphene (3D NG) aerogel;
s3, taking 10mg of 3D NG aerogel in 50ml of distilled water, placing the suspension on a magnetic stirrer for stirring for 24 hours after ultrasonic treatment for 1 hour, filtering the solution, and carrying out freeze-drying treatment on filter residues by using a vacuum freeze dryer to finally obtain 3D NG with better dispersibility;
s4, firstly weighing a certain mass of Cellulose Acetate (CA), dissolving the cellulose acetate in an N, N-dimethylacetamide/acetone mixed solution with the mass ratio of 1:2 to obtain a CA solution with the concentration of 10-30wt%, then adding Polyurethane (PU) with the mass equal to that of the cellulose acetate into the solution, adding 3D NG and boron nitride inorganic nano particles into the PU/CA mixed solution with the mass ratio of 0.1-0.5:100, uniformly stirring the prepared solution for 24 hours at room temperature, then carrying out ultrasonic treatment in an ultrasonic cleaner for 30 minutes, continuing stirring for 1 hour, and repeating the steps for three times;
and S5, connecting a high-voltage power supply between the polyester net and the electrostatic spinning, ejecting the solution obtained in the step S4 from the tip of the capillary by using electrostatic spinning equipment to form graphene nanofibers, uniformly depositing the graphene nanofibers on the polyester net, gathering the polyester net into strips by using a bell mouth, and adding certain twist. Finally, preparing the graphene nanofiber blended yarn through a subsequent yarn forming process. The spinning voltage is 18kV, the receiving distance is 15cm, the push injection speed is 0.08mm/min, the thickness of the polyester net is 2mm, the breadth is 20cm, and the conveying speed of the polyester net is 140cm/min.
Comparative example 2
The procedure of example 2 was followed except that urea was replaced with melamine in step S2.
Comparative example 3
In step S4, the procedure is the same as in example 2, except that urea is not added.
Fig. 3-5 are transmission electron microscopy images of prepared graphene of example 2, comparative example 2 and comparative example 3, respectively, from which it is understood that the nitrogen-doped graphene prepared in example 2 forms rather disordered sheets for some small graphene monolayers or few layers, the nitrogen-doped graphene prepared in comparative example 2 shows large, thin and corrugated sheets, and the comparative example 3 is a thin layer of large transparent graphene sheet. Compared to comparative example 3 without doping, graphene nanoplatelets nitrogen doped with urea or melamine have more edge structures. In addition, compared with melamine, the nitrogen doped graphene obtained by using urea has a richer edge structure, smaller size and larger specific surface area, and has an important promotion effect on the antibacterial effect.
Fig. 6 is a raman spectrum of the prepared graphene of example 2, comparative example 2 and comparative example 3 of the present invention. The data show that the G band (caused by planar motion of sp2 hybridized carbon atoms) position in graphite is 1593cm -1 Where the oxidation was followed by a shift to 1604 cm-1. After reduction and doping treatments, the G-band positions of the graphene prepared in example 2, comparative example 2 and comparative example 3 were shifted to 1583cm, respectively -1 ，1584cm -1 And 1587cm -1 . After doping, is positioned at 1363cm -1 The D band peak representing sp3 hybridized defect at this point shifts to 1340cm -1 . In addition, the relative strengths of the D and G bands of comparative example 3, comparative example 2 and example 2 (I D /I G ) The gradual increase indicates that nitrogen doping generates defects in the graphene structure, and that defects are the greatest when urea is used as the dopant. The nitrogen doped graphene rich in defects is beneficial to optimizing the electronic structure of the graphene, electrons generated during bacterial respiratory metabolism can be efficiently captured, and the intrinsic antibacterial capacity of the graphene is improved.
Example 3
S1, firstly, ultrasonically dispersing Graphene Oxide (GO) powder with a certain mass into 100ml of deionized water to finally obtain 5mg/ml of GO solution, mixing the solution with 20ml of ascorbic acid solution with a concentration of 150mg/ml, stirring by using a magnetic stirrer, pouring the solution into a customized glass mold when the solution is full of bubbles and the color turns from black to yellow, placing the glass mold into a 60 ℃ oven for standing, adding deionized water into the mold after hydrogel is formed, and then continuously standing for 10 hours to obtain partially reduced GO hydrogel;
s2, putting the GO hydrogel obtained in the step S1 into a refrigerator at 60-80 ℃ below zero, fully freezing, taking out, compressing the hydrogel thawed at room temperature to 1cm by using a tablet press, putting into a muffle furnace, adding 5mg of urea, stopping heating to 350 ℃ at 2 ℃/min, preserving heat for 2 hours, and naturally cooling to finally obtain the three-dimensional graphene (3D NG) aerogel;
s3, taking 10mg of 3D NG aerogel in 50ml of distilled water, placing the suspension on a magnetic stirrer for stirring for 24 hours after ultrasonic treatment for 1 hour, filtering the solution, and carrying out freeze-drying treatment on filter residues by using a vacuum freeze dryer to finally obtain 3D NG with better dispersibility;
s4, firstly weighing a certain mass of Cellulose Acetate (CA), dissolving the cellulose acetate in an N, N-dimethylacetamide/acetone mixed solution with the mass ratio of 1:2 to obtain a CA solution with the concentration of 12wt%, then adding Polyurethane (PU) with the mass equal to that of the cellulose acetate into the solution, adding 3D NG and boron nitride inorganic nano particles into the PU/CA mixed solution with the mass ratio of 0.5:100, uniformly stirring the prepared solution for 24 hours at room temperature, then carrying out ultrasonic treatment in an ultrasonic cleaner for 30 minutes, continuing stirring for 1 hour, and repeating the steps for three times;
and S5, connecting a high-voltage power supply between the polyester net and the electrostatic spinning, ejecting the solution obtained in the step S4 from the tip of the capillary by using electrostatic spinning equipment to form graphene nanofibers, uniformly depositing the graphene nanofibers on the polyester net, gathering the polyester net into strips by using a bell mouth, and adding certain twist. Finally, preparing the graphene nanofiber blended yarn through a subsequent yarn forming process. The spinning voltage is 18kV, the receiving distance is 15cm, the push injection speed is 0.08mm/min, the thickness of the polyester net is 2mm, the breadth is 20cm, and the conveying speed of the polyester net is 140cm/min.
Comparative example 4
In step S4, the procedure was the same as in example 3, except that cellulose acetate was not added.
Comparative example 5
The procedure of example 3 was repeated except that boron nitride was not added in step S4.
In order to test the antibacterial effect of the samples prepared by the invention, the antibacterial rate of the samples is tested by using a vibration method: raw cotton fabric (1 cm. Times.1 cm) was used as a control sample and a film (1 cm. Times.1 cm) prepared by electrospinning was cut into a certain size, and placed in a flask, and 70mL of LPBS buffer and 5mL of diluted inoculum solution were added. Then, the mixture was shaken on a shaker at 37℃and 120rpm for 18 hours. After a prescribed time, 100. Mu.L of the bacterial suspension diluted to an appropriate multiple was taken, uniformly coated on the surface of the solid medium, and cultured in a sterile environment at a constant temperature of 37℃for 24 hours. Single colonies of the solid medium were counted and the plate count was averaged three times.
The antibacterial rate calculation formula:
wherein: antibacterial ratio of Y-style
W t Mean value of viable bacteria concentration after 18h shaking contact of control sample
Q t Average value of viable bacteria concentration of antibacterial fabric after 18h vibration contact
FIG. 7 is a graph showing the antibacterial activity of the samples prepared according to example 3 of the present invention and comparative examples 1, 2, 4 and 5 against Staphylococcus aureus and Escherichia coli (corresponding data are shown in Table 1). As can be seen from the figure, the antibacterial rate of the samples prepared in comparative examples 1, 2, 4 and 5 against Staphylococcus aureus and Escherichia coli was significantly lower than that in example 3. The three-dimensional structure of the graphene in the comparative example 1 is not obvious, so that the specific surface area of the material is reduced, the contact with bacteria is never reduced, the cutting efficiency of the bacteria is reduced, and the antibacterial effect is not achieved; in comparative example 2, although melamine is used as a doping agent to carry out nitrogen doping on graphene, the final antibacterial rate is low, and we hypothesize that the effect of optimizing the electronic structure of graphene by taking urea as the doping agent is better, so that electrons generated during bacterial respiratory metabolism can be effectively captured, and the intrinsic antibacterial capacity of the fiber can be improved; cellulose acetate and boron nitride were absent from comparative examples 4 and 5, respectively, and their antibacterial ability was also poor because cellulose acetate had a certain antibacterial ability, and boron nitride had a bactericidal effect comparable to that of antibiotics because of its special structure. Therefore, the three-dimensional nitrogen doped graphene, the cellulose acetate and the boron nitride have a certain synergistic effect, so that the antibacterial capability of the graphene fiber is improved together.
Table 1 antibacterial ratio of inventive example 3 and comparative examples 1, 2, 4 and 5 preparation of samples against staphylococcus aureus and escherichia coli
Claims (10)
1. The preparation method for preparing the antibacterial graphene fiber through electrostatic spinning is characterized by comprising the following preparation steps:
s1, firstly, ultrasonically dispersing Graphene Oxide (GO) powder with a certain mass into 100ml of deionized water to finally obtain 2-5mg/ml of GO solution, mixing the GO solution with 20ml of ascorbic acid solution with the concentration of 50-150mg/ml, stirring by using a magnetic stirrer, pouring the solution into a customized glass mold when the solution is full of bubbles and the color turns from black to yellow, placing the glass mold into a baking oven at 60 ℃, standing, adding deionized water into the mold after hydrogel is formed, and then continuously standing for 10 hours to obtain partially reduced GO hydrogel;
s2, putting the GO hydrogel obtained in the step S1 into a refrigerator at the temperature of minus 60-80 ℃, fully freezing, taking out, compressing the hydrogel thawed at room temperature to 1cm by using a tablet press, putting into a muffle furnace, adding urea with a certain mass, heating to 150-350 ℃ at a certain speed, stopping, preserving heat for 2-6h, and naturally cooling to finally obtain the three-dimensional graphene (3D NG) aerogel;
s3, taking 10mg of 3D NG aerogel in 50ml of distilled water, placing the suspension on a magnetic stirrer for stirring for 24 hours after ultrasonic treatment for 1 hour, filtering the solution, and carrying out freeze-drying treatment on filter residues by using a vacuum freeze dryer to finally obtain 3D NG with better dispersibility;
s4, firstly weighing a certain mass of Cellulose Acetate (CA), dissolving the cellulose acetate in an N, N-dimethylacetamide/acetone mixed solution with the mass ratio of 1:2 to obtain a CA solution with the concentration of 10-30wt%, then adding Polyurethane (PU) with the mass equal to that of the cellulose acetate into the solution, adding 3D NG and boron nitride inorganic nano particles into the PU/CA mixed solution with the mass ratio of 0.1-0.5:100, uniformly stirring the prepared solution for 24 hours at room temperature, then carrying out ultrasonic treatment in an ultrasonic cleaner for 30 minutes, continuing stirring for 1 hour, and repeating the steps for three times;
and S5, connecting a high-voltage power supply between the polyester net and the electrostatic spinning equipment, utilizing the electrostatic spinning equipment to eject the solution obtained in the step S4 from the tip of the capillary to form graphene nanofibers, uniformly depositing the graphene nanofibers on the polyester net, gathering the polyester net into strips by utilizing a bell mouth, adding a certain twist, and preparing the graphene nanofiber blended yarn through a subsequent yarn forming process, wherein the spinning voltage is 18kV, the receiving distance is 15cm, the pushing speed is 0.08mm/min, the thickness of the polyester net is 2mm, the breadth is 20cm, and the conveying speed of the polyester net is 140cm/min.
2. The method for preparing the antibacterial graphene fiber by electrostatic spinning according to claim 1, wherein the method comprises the following steps: the concentration of the GO solution in the step S1 is 2mg/ml.
3. The method for preparing the antibacterial graphene fiber by electrostatic spinning according to claim 2, wherein: the concentration of the ascorbic acid solution in the step S1 is 100mg/ml.
4. A method for preparing an antibacterial graphene fiber by electrospinning according to claim 3, wherein: the refrigerator temperature in the step S2 is-80 ℃.
5. The method for preparing the antibacterial graphene fiber by electrostatic spinning according to claim 4, wherein: and in the step S2, the temperature of the muffle furnace is 300 ℃, the temperature rising speed is 2 ℃/min, and the heat preservation time is 3h.
6. The method for preparing the antibacterial graphene fiber by electrostatic spinning according to claim 5, wherein the method comprises the following steps: the concentration of the CA solution in step S4 was 20wt%.
7. The method for preparing the antibacterial graphene fiber by electrostatic spinning according to claim 6, wherein: in the step S4, the mass ratio of the 3D NG to the boron nitride is 1.2:0.5.
8. the method for preparing the antibacterial graphene fiber by electrostatic spinning according to claim 7, wherein: the mass ratio of the inorganic nano particles to the total mass of PU/CA in the step S4 is 0.1:100.
9. The method for preparing the antibacterial graphene fiber by electrostatic spinning according to claim 7, wherein: the mass ratio of the inorganic nano particles to the total mass of PU/CA in the step S4 is 0.3:100.
10. The antibacterial graphene fiber prepared by the preparation method of any one of claims 1 to 9.
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| WO2015142159A1 (en) * | 2014-03-17 | 2015-09-24 | Universiti Kebangsaan Malaysia | A method for preparing a cellulose based material |
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