CN113186655A - Nano carbon nitride fiber film and preparation method thereof - Google Patents
Nano carbon nitride fiber film and preparation method thereof Download PDFInfo
- Publication number
- CN113186655A CN113186655A CN202110366618.XA CN202110366618A CN113186655A CN 113186655 A CN113186655 A CN 113186655A CN 202110366618 A CN202110366618 A CN 202110366618A CN 113186655 A CN113186655 A CN 113186655A
- Authority
- CN
- China
- Prior art keywords
- carbon nitride
- water
- alkali metal
- metal salt
- preparation
- 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.)
- Pending
Links
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000835 fiber Substances 0.000 title claims abstract description 8
- 229910021392 nanocarbon Inorganic materials 0.000 title abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000009987 spinning Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000012528 membrane Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000002121 nanofiber Substances 0.000 claims abstract description 23
- -1 alkali metal salt Chemical class 0.000 claims abstract description 18
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 16
- 239000012046 mixed solvent Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 230000003385 bacteriostatic effect Effects 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- 230000000694 effects Effects 0.000 claims abstract description 8
- 230000001954 sterilising effect Effects 0.000 claims abstract description 7
- 238000004659 sterilization and disinfection Methods 0.000 claims abstract description 7
- 230000001699 photocatalysis Effects 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000011363 dried mixture Substances 0.000 claims abstract description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- 235000011181 potassium carbonates Nutrition 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000010453 quartz Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000001523 electrospinning Methods 0.000 claims description 5
- 239000011888 foil Substances 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004693 Polybenzimidazole Substances 0.000 claims description 2
- 239000004697 Polyetherimide Substances 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 claims description 2
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920002480 polybenzimidazole Polymers 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920001601 polyetherimide Polymers 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 239000004626 polylactic acid Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 18
- 241000588724 Escherichia coli Species 0.000 abstract description 9
- 241000589517 Pseudomonas aeruginosa Species 0.000 abstract description 9
- 241000191967 Staphylococcus aureus Species 0.000 abstract description 9
- 241000194017 Streptococcus Species 0.000 abstract description 9
- 238000000227 grinding Methods 0.000 abstract description 5
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 230000002147 killing effect Effects 0.000 abstract description 2
- 244000052769 pathogen Species 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000002086 nanomaterial Substances 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 239000003242 anti bacterial agent Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- 241000700605 Viruses Species 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000002120 nanofilm Substances 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 239000013641 positive control Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000013642 negative control Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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
-
- 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
-
- 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
Abstract
The invention relates to a recyclable antibacterial nano carbon nitride fiber film and a preparation method thereof. The method comprises the following steps: (1) and mixing and heating the precursor and the alkali metal salt according to a certain proportion until the water is evaporated to dryness to obtain a mixture. Grinding and drying, and heating the dried mixture to obtain graphite-phase carbon nitride; (2) adding the modified carbon nitride into a mixed solvent of ethanol and water, carrying out ultrasonic crushing for 1-6 hours, adding high polymer molecules with the mass of 50-100 times that of the carbon nitride, and stirring until a uniform spinning solution is formed; (3) and (3) performing electrostatic spinning on the spinning solution obtained in the step (2) to prepare the recyclable carbon nitride nanofiber membrane with photocatalytic sterilization effect. The antibacterial nano material prepared by the method has high antibacterial rate and excellent recycling performance. The bacteriostatic carbon nitride fiber membrane has obvious inhibiting and killing effects on pathogens such as escherichia coli, staphylococcus aureus, streptococcus, pseudomonas aeruginosa and the like, and can be recycled.
Description
Technical Field
The invention belongs to the field of chemical engineering and high polymer materials, and particularly relates to a recyclable antibacterial nano carbon nitride fiber film and a preparation method thereof.
Background
The electrostatic spinning technology is a process of spinning a polymer solution under the action of high-voltage static electricity. The nano-fiber with controllable size, high specific surface area and high porosity can be obtained by utilizing the technology, and the nano-fiber has wide application in the fields of biomedicine, air filter materials, protective articles and the like, sensors, medical auxiliary materials and the like. The nanofiber membrane obtained by utilizing the electrostatic spinning technology has the advantages of light weight, good permeability, proper cost and strong electrostatic adsorption effect, and is very suitable for medical materials such as protective clothing, masks and the like. However, the nanofiber membrane has low reuse rate in the using process, and particularly has no repeatability and higher cost in the adsorption process of pathogenic bacteria such as bacteria, viruses and the like, so that the development of the reusable nanofiber membrane is necessary to solve the problems of short use, serious resource waste and the like of the existing disposable medical filter material.
Disclosure of Invention
In view of the above-mentioned problems, the present invention aims to provide a method for preparing a bacteriostatic carbon nitride nanofiber membrane capable of being recycled and its use. The method of the invention utilizes the electrostatic spinning technology to achieve the effect of bacteriostasis and sterilization by synthesizing the carbon nitride spinning solution with visible light response, thereby realizing the repeated use of the filter material. The method can overcome the defects of poor circulation performance, poor antibacterial effect and the like of the traditional filter material. The filter material has obvious inhibiting and killing effects on pathogens such as escherichia coli, staphylococcus aureus, streptococcus, pseudomonas aeruginosa and the like through free radicals and cavities generated by carbon nitride under the illumination condition, and can be repeatedly recycled. In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a carbon fiber nano nitride film comprises the following steps:
(1) preparation of alkali metal salt modified carbon nitride
Adding the carbon nitride precursor and potassium carbonate into 50mL of water according to a certain proportion, magnetically stirring, heating to 80 ℃ until the water is evaporated to dryness, and obtaining a mixture. And grinding the mixture. Vacuum drying at 60 deg.C for 12 hr, placing the dried mixture into quartz crucible, sealing with aluminum foil paper, heating in nitrogen atmosphere, and reacting to obtain graphite phase carbon nitride catalyst.
(2) Preparation of electrospinning solution
Adding a certain mass of the modified carbon nitride into a mixed solvent of ethanol and water, the mass of the mixed solvent is 500-2000 times that of the modified carbon nitride, carrying out ultrasonic crushing for 1-6 hours, adding high polymer molecules, the mass of which is 50-100 times that of the carbon nitride, and carrying out magnetic stirring for 48 hours until a uniform viscous spinning solution is formed.
(3) Preparation of bacteriostatic carbon nitride nanofiber membrane
And (3) performing electrostatic spinning on the spinning solution obtained in the step (2) to prepare the recyclable carbon nitride nanofiber membrane with photocatalytic sterilization effect. Spinning positive voltage is 3-8 kv, negative voltage is-5-9 kv, and propelling speed is 0.5-3 mL/min.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a preparation method and application of a recyclable antibacterial nano carbon nitride film, which comprises the following steps:
(1) preparation of alkali metal salt modified carbon nitride
Adding the carbon nitride precursor and the alkali metal salt into 50mL of water according to a certain proportion, magnetically stirring, heating to 80 ℃ until the water is evaporated to dryness, and obtaining a mixture. And grinding the mixture. Vacuum drying at 60 deg.C for 12h, placing the dried mixture into a quartz crucible, sealing with aluminum foil paper, heating in nitrogen atmosphere, and reacting to obtain graphite phase carbon nitride catalyst.
(2) Preparation of electrospinning solution
Adding a certain mass of the modified carbon nitride into a mixed solvent of ethanol and water, the mass of the mixed solvent is 500-2000 times that of the modified carbon nitride, carrying out ultrasonic crushing for 1-6 hours, adding high polymer molecules, the mass of which is 50-100 times that of the carbon nitride, and carrying out magnetic stirring for 48 hours until a uniform viscous spinning solution is formed.
(3) Preparation of bacteriostatic carbon nitride nanofiber membrane
And (3) performing electrostatic spinning on the spinning solution obtained in the step (2) to prepare the recyclable carbon nitride nanofiber membrane with photocatalytic sterilization effect. Spinning positive voltage is 3-8 kv, negative voltage is-5-9 kv, and propelling speed is 0.5-3 mL/min.
The modified carbon nitride photocatalyst utilized in the invention has the characteristic of visible light effect, is non-toxic and green, can generate a large amount of electrons and holes under visible light, quickly kills various bacteria and viruses adsorbed by the filter material, and realizes the reusability of the filter material.
As a preferred technical solution of the method of the present invention, the precursor in step (1) comprises any one or a combination of at least two of urea, melamine, dicyandiamide, thiourea and cyanamide, preferably melamine.
The cation of the alkali metal salt used in the step (1) comprises one or more of potassium carbonate, sodium carbonate, lithium carbonate, potassium bicarbonate, sodium bicarbonate, potassium acetate and sodium acetate, and is preferably potassium carbonate.
Preferably, the mass ratio of the precursor to the alkali metal salt in the step (1) is 10: (0.1 to 1), for example, 10:0.1, 10:0.2, 10:0.4, 10:0.5, 10:0.7, 10:0.9, 10:1, etc. If the mass ratio is more than 10:1, the carbon content in the system is increased, the active sites of the carbon nitride are covered, the antibacterial performance of the nano film is reduced, and the cyclic usability of the nano film is reduced; if the mass ratio is less than 10:0.1, the carbon nitride is difficult to be correspondingly regulated and controlled. More preferably, the mass ratio of the precursor to the alkali metal salt is 10 (0.2-0.7).
Preferably, the heating temperature in the step (1) is 500-800 ℃, preferably 550-600 ℃.
Preferably, in the step (2), the mass ratio of the carbon nitride to the solvent and the high polymer is 1: (500-2000): (50 to 100), for example, 1: 500: 50,1: 700: 70,1: 800: 60,1: 1000:70,1: 1500: 90,1: 1500: 70,1: 1900: 100,1: 2000: 100, etc., preferably: 1:1000: 70.
preferably, in the step (2), the volume ratio of ethanol to water in the mixed solvent is 1: (0 to 10), for example, 1:0,1: 1,1: 3,1: 5,1: 7,1: 9,1: 10, preferably 1: 1.
preferably, in step (2), the polymer used comprises at least one of polyamide, polyvinyl butyral, polyacrylamide, polyacrylonitrile, polybenzimidazole, polycarbonate, polycaprolactone, polyetherimide, polyethylene oxide, polyethylene terephthalate, polyimide, polylactic acid, polyurethane, polyvinyl imidazole, polyvinyl pyrrolidone, polyvinyl alcohol, and preferably polyvinyl butyral.
Preferably, in the step (3), the positive voltage for spinning is 3 to 8kv, such as 3kv, 3.3kv, 4kv, 4.4kv, 5kv, 5.2kv, 6kv, 7kv, 8kv, preferably 4 to 6 kv.
Preferably, in step (3), the negative voltage is-5 to-9 kv, such as-5 kv, -5.2kv, -6kv, -6.2kv, -7kv, -7.1kv, -7.5kv, -8kv, -8.2kv, -8.5kv, -9kv, and the like, preferably-6 to-8 kv.
Preferably, in step (3), the propelling speed is 0.5-3 mL/min, such as 0.5mL/min, 0.9mL/min, 1.5mL/min, 2.0mL/min, 2.2mL/min, 2.5mL/min, 3.0mL/min, etc., preferably 1-2.5 mL/min.
As a further preferred technical solution of the method of the present invention, the method comprises the steps of:
(1) preparation of alkali metal salt modified carbon nitride
Adding a carbon nitride precursor and potassium carbonate into 50mL of water according to a mass ratio of 10 (0.2-0.7), magnetically stirring, heating to 80 ℃, and evaporating until the water is evaporated to dryness to obtain a mixture. And grinding the mixture. Vacuum drying at 60 deg.c for 12 hr, loading the mixture into quartz crucible, sealing with aluminum foil paper, heating to 550-600 deg.c in nitrogen atmosphere, and further reaction to obtain graphite phase carbon nitride catalyst.
(2) Preparation of electrospinning solution
Adding a certain mass of the modified carbon nitride into a mixed solvent of ethanol and water (the volume ratio is 1:1), carrying out ultrasonic crushing for 1-6 hours, adding a certain mass of polyvinyl butyral, carrying out magnetic stirring for 48 hours until a uniform viscous spinning solution is formed, wherein the mass ratio of the carbon nitride to the ethanol to the polyvinyl butyral is 1:1000: 70.
(3) Preparation of bacteriostatic carbon nitride nanofiber membrane
And (3) performing electrostatic spinning on the spinning solution obtained in the step (2) to prepare the recyclable carbon nitride nanofiber membrane with photocatalytic sterilization effect. Spinning positive voltage is 4-6 kv, negative voltage is-6-8 kv, and propelling speed is 1-2.5 mL/min.
The preparation method of the bacteriostatic carbon nitride nanofiber membrane is illustrated by the following specific examples. The compounds in the following examples can be prepared directly according to the existing methods, but of course, in other examples, they can be directly commercially available, and are not limited thereto.
Example 1
(1) Preparation of alkali metal salt modified carbon nitride
Adding 10g of urea and 0.1g of potassium carbonate into 50mL of water, magnetically stirring, heating to 80 ℃ until the water is evaporated to dryness, and thus obtaining a mixture. And grinding the mixture. Vacuum drying at 60 deg.C for 12h, placing the dried mixture into a quartz crucible, sealing with aluminum foil paper, heating to 500 deg.C under nitrogen atmosphere, and reacting for 4h to obtain graphite phase carbon nitride catalyst.
(2) Preparation of electrospinning solution
Adding 20mg of modified carbon nitride into a mixed solvent of 10g of ethanol and water (volume ratio is 1:1), carrying out ultrasonic crushing for 1-6 hours, adding 1g of polyvinyl butyral, and carrying out magnetic stirring for 48 hours until a uniform viscous spinning solution is formed.
(3) Preparation of bacteriostatic carbon nitride nanofiber membrane
And (3) performing electrostatic spinning on the spinning solution obtained in the step (2) to prepare the recyclable carbon nitride nanofiber membrane with photocatalytic sterilization effect. The spinning positive voltage is 3kv, the negative voltage is-5 kv, and the advancing speed is 0.5 mL/min.
And (3) performance detection:
the obtained antibacterial nanofiber membrane is tested for the antibacterial rate and the cycle performance of the antibacterial rate on escherichia coli, staphylococcus aureus, streptococcus and pseudomonas aeruginosa by a shaking oscillation method, the test result shows that the antibacterial rate on the four bacteria is 92.23%, 96.21%, 95.26% and 92.15%, and the fiber membrane after being used is irradiated by visible light for 30min, so that the fiber membrane can be repeatedly used. The antibacterial effect is not reduced after the antibacterial agent is repeatedly used for four times. The inhibition rate is determined by the minimum inhibition concentration, and the formula is as follows:
bacteriostatic rate (%) - (positive control OD value-test OD value)/(positive control OD value-negative control OD value) × 100
Example 2
The preparation method and conditions were the same as in example 1, except that:
in the step (1), the using amount of potassium carbonate is 1 g;
in the step (1), the heating temperature is 800 ℃;
in the step (2), the dosage of the mixed solvent is changed to 40g, the volume ratio of the ethanol to the water is 1:2, and the dosage of the polyvinyl butyral is 2 g;
in the step (3), the spinning positive voltage is 5kv, the negative voltage is-7 kv, and the advancing speed is 0.5 mL/min.
The same detection method as that of the example 1 is adopted, the bacteriostasis rates of the antibacterial agents to escherichia coli, staphylococcus aureus, streptococcus and pseudomonas aeruginosa are 91.13%, 94.46%, 95.24% and 91.18% respectively, and the antibacterial effects are not reduced after the antibacterial agents are repeatedly used for four times.
Example 3
The preparation method and conditions were the same as in example 1, except that:
in the step (1), the alkali metal salt is changed into potassium bicarbonate;
in the step (2), the dosage of the mixed solvent is changed to 20g, the volume ratio of ethanol to water is 1:0.2, and the dosage of the polyvinyl butyral is 1.4 g;
in the step (3), the spinning positive voltage is 5kv, the negative voltage is-8 kv, and the advancing speed is 1 mL/min.
The same detection method as that of the example 1 is adopted, the bacteriostasis rates of the antibacterial agents to escherichia coli, staphylococcus aureus, streptococcus and pseudomonas aeruginosa are respectively 96.12%, 95.45%, 95.15% and 97.56%, and the antibacterial effect is not reduced after the antibacterial agents are repeatedly used for four times.
Example 4
The preparation method and conditions were the same as in example 1, except that:
in the step (1), the alkali metal salt is changed into lithium carbonate, and the using amount is 0.8 g;
in the step (2), the dosage of the mixed solvent is changed to 20g, the volume ratio of ethanol to water is 1:2, and polyvinyl butyral is changed to polyvinyl alcohol;
in the step (3), the spinning positive voltage is 5kv, the negative voltage is-8 kv, and the advancing speed is 1 mL/min.
The same detection method as that of the example 1 is adopted, the bacteriostasis rates of the antibacterial agents to escherichia coli, staphylococcus aureus, streptococcus and pseudomonas aeruginosa are respectively 83.13%, 85.91%, 88.24% and 90.13%, and the antibacterial effect is not reduced after the antibacterial agents are repeatedly used for four times.
Example 5
The preparation method and conditions were the same as in example 1, except that:
in the step (1), the alkali metal salt is a mixture of 0.5g of potassium carbonate and 0.5g of lithium carbonate;
in the step (2), the dosage of the mixed solvent is changed to 30g, the volume ratio of ethanol to water is 1:5, and the polyvinyl butyral is changed to polyimide;
in the step (3), the spinning positive voltage is 6kv, the negative voltage is-7 kv, and the advancing speed is 2 mL/min.
The same detection method as that of the example 1 is adopted, the bacteriostasis rates of the antibacterial agents to escherichia coli, staphylococcus aureus, streptococcus and pseudomonas aeruginosa are 92.16%, 94.34%, 95.13% and 96.72% respectively, and the antibacterial effect is not reduced after the antibacterial agents are repeatedly used for four times.
Example 6
The preparation method and conditions were the same as in example 1, except that:
in the step (1), the using amount of potassium carbonate is 0.8 g;
in the step (2), the dosage of the mixed solvent is changed to 25g, the volume ratio of ethanol to water is 1:7, and the polyvinyl butyral is changed to polyvinylpyrrolidone;
in the step (3), the spinning positive voltage is 7.5kv, the negative voltage is-8.5 kv, and the advancing speed is 3 mL/min.
The same detection method as that of the example 1 is adopted, the bacteriostasis rates of the antibacterial agents to escherichia coli, staphylococcus aureus, streptococcus and pseudomonas aeruginosa are respectively 90.12%, 91.33%, 90.24% and 93.15%, and the antibacterial effects are not reduced after the antibacterial agents are repeatedly used for four times.
Comparative example 1: antibacterial cycling performance of traditional nanofiber membranes
1g of polyvinyl butyral was added to a mixed solvent of 10g of ethanol and water (volume ratio of 1:1), and magnetically stirred for 48 hours until a uniform viscous dope was formed.
And (3) carrying out electrostatic spinning on the obtained spinning solution, wherein the spinning positive voltage is 3kv, the spinning negative voltage is-5 kv, and the propelling speed is 0.5 mL/min.
And (3) performance detection:
the obtained bacteriostatic nanofiber membrane is tested for the bacteriostatic rate and the cycle performance of the bacteriostatic nanofiber membrane on escherichia coli, staphylococcus aureus, streptococcus and pseudomonas aeruginosa by a shaking oscillation method, and test results show that the bacteriostatic rate on four bacteria is respectively 50.12%, 55.47%, 55.63% and 60.12%, and the bacteriostatic nanofiber membrane does not have repeated usability.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (9)
1. A nanometer carbon nitride fiber film and a preparation method thereof are characterized by comprising the following steps:
(1) preparing carbon nitride modified by alkali metal salt, namely adding a carbon nitride precursor and the alkali metal salt into 50mL of water according to a certain proportion, magnetically stirring, heating to 80 ℃ until the water is evaporated to dryness to obtain a mixture; vacuum drying the ground mixture at 60 ℃ for 12 hours, putting the dried mixture into a quartz crucible, sealing the quartz crucible by using aluminum foil paper, heating the quartz crucible in a nitrogen atmosphere, and continuing to react to obtain a graphite-phase carbon nitride catalyst;
(2) preparing an electrostatic spinning solution, namely adding a certain mass of the modified carbon nitride into a mixed solvent of ethanol and water, carrying out ultrasonic crushing for 1-6 hours, then adding high polymer molecules, and carrying out magnetic stirring for 48 hours until a uniform viscous spinning solution is formed;
(3) and (3) preparing the bacteriostatic carbon nitride nanofiber membrane, namely performing electrostatic spinning on the spinning solution obtained in the step (2) to prepare the recyclable carbon nitride nanofiber membrane with photocatalytic sterilization effect.
2. The method according to claim 1, wherein the carbon nitride precursor is selected from any one of urea, melamine, dicyandiamide, thiourea and cyanamide or a combination of at least two of the above.
3. The method according to claim 1, wherein the cation of the alkali metal salt comprises potassium carbonate, sodium carbonate, lithium carbonate, potassium bicarbonate, sodium bicarbonate, potassium acetate, sodium acetate, or a combination of one or more thereof.
4. The method according to claim 1, wherein the heating temperature is 500 to 800 ℃.
5. The method according to claim 1, wherein the mass ratio of the precursor to the alkali metal salt is 10: (0.1 to 1).
6. The method according to claim 1, wherein the mass ratio of the carbon nitride to the hydroalcoholic mixed solvent and the high polymer is 1: (500-2000): (50-100).
7. The method according to claim 1, wherein the volume ratio of the ethanol to water is 1: (0-10).
8. The method of claim 1, wherein the high polymer comprises one or more of polyamide, polyvinyl butyral, polyacrylamide, polyacrylonitrile, polybenzimidazole, polycarbonate, polycaprolactone, polyetherimide, polyethylene oxide, polyethylene terephthalate, polyimide, polylactic acid, polyurethane, polyvinyl imidazole, polyvinyl pyrrolidone, and polyvinyl alcohol.
9. The method according to claim 1, wherein the electrospinning has a positive voltage of 3 to 8kv, a negative voltage of-5 to-9 kv, and a forwarding speed of 0.5 to 3 mL/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110366618.XA CN113186655A (en) | 2021-04-06 | 2021-04-06 | Nano carbon nitride fiber film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110366618.XA CN113186655A (en) | 2021-04-06 | 2021-04-06 | Nano carbon nitride fiber film and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113186655A true CN113186655A (en) | 2021-07-30 |
Family
ID=76974751
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110366618.XA Pending CN113186655A (en) | 2021-04-06 | 2021-04-06 | Nano carbon nitride fiber film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113186655A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114959950A (en) * | 2022-06-15 | 2022-08-30 | 浙江毅聚新材料有限公司 | Preparation process of carbon fiber |
Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104772160A (en) * | 2015-04-17 | 2015-07-15 | 北京师范大学 | Carbon nitride photocatalytic activity nano fiber membrane and preparation method thereof |
| CN104944392A (en) * | 2014-03-25 | 2015-09-30 | 中国科学院大连化学物理研究所 | Mass preparation method of graphite-phase carbon nitride nanosheets |
| CN105126893A (en) * | 2015-08-31 | 2015-12-09 | 中国科学院过程工程研究所 | Graphite-phase carbon nitride (g-C3N4) material and preparation method and application thereof |
| CN106319673A (en) * | 2016-08-19 | 2017-01-11 | 浙江理工大学 | Composite photocatalytic fibers and preparation method thereof |
| CN107034585A (en) * | 2017-04-19 | 2017-08-11 | 江苏大学 | A kind of g C3N4Nanofiber antibacterial film and preparation method thereof and purposes |
| CN107473191A (en) * | 2017-07-19 | 2017-12-15 | 天津大学 | Method for preparing three-dimensional graphite phase carbon nitride with cyano group by salt assistance |
| CN108636136A (en) * | 2018-05-11 | 2018-10-12 | 江苏大学 | A kind of Pd/C3N4The preparation method and application of@biomass carbon composite fiber membranes |
| CN109473628A (en) * | 2018-11-14 | 2019-03-15 | 东华大学 | A kind of silicon-nitridation carbon compound cathode materials and its preparation and application |
| CN109666977A (en) * | 2019-02-25 | 2019-04-23 | 牟富书 | A kind of anti-bacterial fibre preparation method |
| CN109675450A (en) * | 2018-12-26 | 2019-04-26 | 中国科学院深圳先进技术研究院 | A kind of antibacterial composite nano-fiber membrane and its preparation method and application |
| CN110560130A (en) * | 2019-09-12 | 2019-12-13 | 哈尔滨工业大学 | preparation method of cerium dioxide nanosphere-carbon nitride composite visible-light-driven photocatalyst |
| CN110813351A (en) * | 2019-10-28 | 2020-02-21 | 北京理工大学 | Preparation method of graphite phase carbon nitride catalyst |
| CN111172622A (en) * | 2019-12-31 | 2020-05-19 | 赵梓权 | Photocatalytic biomass fiber and preparation method thereof |
| CN111286175A (en) * | 2020-03-16 | 2020-06-16 | 赵梓权 | Degradable spinning raw material, degradable fiber membrane and degradable protective cover |
| US20200384422A1 (en) * | 2017-11-28 | 2020-12-10 | G2O Water Technologies Limited | Graphene or Graphene Derivative Membrane |
| CN112495414A (en) * | 2020-11-19 | 2021-03-16 | 中国科学院山西煤炭化学研究所 | Carbon nitride supported catalyst for preparing low-carbon mixed alcohol from synthesis gas and preparation method and application thereof |
-
2021
- 2021-04-06 CN CN202110366618.XA patent/CN113186655A/en active Pending
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104944392A (en) * | 2014-03-25 | 2015-09-30 | 中国科学院大连化学物理研究所 | Mass preparation method of graphite-phase carbon nitride nanosheets |
| CN104772160A (en) * | 2015-04-17 | 2015-07-15 | 北京师范大学 | Carbon nitride photocatalytic activity nano fiber membrane and preparation method thereof |
| CN105126893A (en) * | 2015-08-31 | 2015-12-09 | 中国科学院过程工程研究所 | Graphite-phase carbon nitride (g-C3N4) material and preparation method and application thereof |
| CN106319673A (en) * | 2016-08-19 | 2017-01-11 | 浙江理工大学 | Composite photocatalytic fibers and preparation method thereof |
| CN107034585A (en) * | 2017-04-19 | 2017-08-11 | 江苏大学 | A kind of g C3N4Nanofiber antibacterial film and preparation method thereof and purposes |
| CN107473191A (en) * | 2017-07-19 | 2017-12-15 | 天津大学 | Method for preparing three-dimensional graphite phase carbon nitride with cyano group by salt assistance |
| US20200384422A1 (en) * | 2017-11-28 | 2020-12-10 | G2O Water Technologies Limited | Graphene or Graphene Derivative Membrane |
| CN108636136A (en) * | 2018-05-11 | 2018-10-12 | 江苏大学 | A kind of Pd/C3N4The preparation method and application of@biomass carbon composite fiber membranes |
| CN109473628A (en) * | 2018-11-14 | 2019-03-15 | 东华大学 | A kind of silicon-nitridation carbon compound cathode materials and its preparation and application |
| CN109675450A (en) * | 2018-12-26 | 2019-04-26 | 中国科学院深圳先进技术研究院 | A kind of antibacterial composite nano-fiber membrane and its preparation method and application |
| CN109666977A (en) * | 2019-02-25 | 2019-04-23 | 牟富书 | A kind of anti-bacterial fibre preparation method |
| CN110560130A (en) * | 2019-09-12 | 2019-12-13 | 哈尔滨工业大学 | preparation method of cerium dioxide nanosphere-carbon nitride composite visible-light-driven photocatalyst |
| CN110813351A (en) * | 2019-10-28 | 2020-02-21 | 北京理工大学 | Preparation method of graphite phase carbon nitride catalyst |
| CN111172622A (en) * | 2019-12-31 | 2020-05-19 | 赵梓权 | Photocatalytic biomass fiber and preparation method thereof |
| CN111286175A (en) * | 2020-03-16 | 2020-06-16 | 赵梓权 | Degradable spinning raw material, degradable fiber membrane and degradable protective cover |
| CN112495414A (en) * | 2020-11-19 | 2021-03-16 | 中国科学院山西煤炭化学研究所 | Carbon nitride supported catalyst for preparing low-carbon mixed alcohol from synthesis gas and preparation method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114959950A (en) * | 2022-06-15 | 2022-08-30 | 浙江毅聚新材料有限公司 | Preparation process of carbon fiber |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107754834B (en) | Iodine-doped bismuthyl carbonate nanosheet and molybdenum disulfide-modified carbon nanofiber composite material and preparation method and application thereof | |
| Panthi et al. | Immobilization of Ag3PO4 nanoparticles on electrospun PAN nanofibers via surface oximation: Bifunctional composite membrane with enhanced photocatalytic and antimicrobial activities | |
| Sundarrajan et al. | Fabrication of nanocomposite membranes from nanofibers and nanoparticles for protection against chemical warfare stimulants | |
| Yang et al. | A novel heterojunction photocatalyst, Bi 2 SiO 5/gC 3 N 4: synthesis, characterization, photocatalytic activity, and mechanism | |
| Chou et al. | Novel synthesis of bismuth oxyiodide/graphitic carbon nitride nanocomposites with enhanced visible-light photocatalytic activity | |
| Hou et al. | Electrospun sillenite Bi 12 MO 20 (M= Ti, Ge, Si) nanofibers: general synthesis, band structure, and photocatalytic activity | |
| Yu et al. | Fabrication of a novel visible-light-driven photocatalyst Ag-AgI-TiO2 nanoparticles supported on carbon nanofibers | |
| Yang et al. | Flower-like zinc oxide nanorod clusters grown on spherical cellulose nanocrystals via simple chemical precipitation method | |
| CN101462045B (en) | Composite material of stannic oxide and carbon, and preparation method thereof | |
| CN113186655A (en) | Nano carbon nitride fiber film and preparation method thereof | |
| Kang et al. | Hierarchical ZnO nano-spines grown on a carbon fiber seed layer for efficient VOC removal and airborne virus and bacteria inactivation | |
| Panthi et al. | Electrospun composite nanofibers of polyacrylonitrile and Ag 2 CO 3 nanoparticles for visible light photocatalysis and antibacterial applications | |
| CN106577750A (en) | Preparing method for titanium-dioxide composite nanometer antibacterial material and product thereof | |
| Kumar et al. | Photocatalytic activity of bismuth vanadate for the degradation of organic compounds | |
| Xu et al. | High-efficient visible-light photocatalyst based on graphene incorporated Ag3PO4 nanocomposite applicable for the degradation of a wide variety of dyes | |
| CN110813306A (en) | Zinc ferrite/bismuth tungstate composite catalyst, preparation method thereof and application thereof in waste gas treatment | |
| CN112619659B (en) | Nickel oxide nanosheet and bismuth molybdate nanofiber heterojunction photocatalytic material as well as preparation method and application thereof | |
| Yu et al. | A new fabrication of AgX (X= Br, I)–TiO 2 nanoparticles immobilized on polyacrylonitrile (PAN) nanofibers with high photocatalytic activity and renewable property | |
| CN114522667A (en) | Preparation and application of bismuth-based composite nanofiber adsorbent for removing radioactive iodine gas | |
| CN109603910A (en) | A kind of nano core-shell compound of photo-thermal enhancing degradation chemical warfare agent analogies and its preparation method and application of composite cellulosic membrane | |
| CN112774664A (en) | Nano TiO with photo-thermal synergistic effect2@MnO2Composite material and preparation method and application thereof | |
| Ji et al. | Electrospun organic/inorganic hybrid nanofibers as low-cytotoxicity and recyclable photocatalysts | |
| Tang et al. | Facile hydrothermal-carbonization approach to carbon-modified BiVO4 composites with enhanced photocatalytic activity | |
| Lou et al. | A versatile electrospun polylactic acid nanofiber membrane integrated with halloysite nanotubes for indoor air purification, disinfection, and photocatalytic degradation of pollutants | |
| CN112371084A (en) | Preparation method and application of sterilized activated carbon |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210730 |
|
| RJ01 | Rejection of invention patent application after publication |