CN115613349A - ZnO-loaded fluorinated SiO 2 Fiber, preparation method and application thereof - Google Patents
ZnO-loaded fluorinated SiO 2 Fiber, preparation method and application thereof Download PDFInfo
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- CN115613349A CN115613349A CN202211173238.5A CN202211173238A CN115613349A CN 115613349 A CN115613349 A CN 115613349A CN 202211173238 A CN202211173238 A CN 202211173238A CN 115613349 A CN115613349 A CN 115613349A
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- 229910004298 SiO 2 Inorganic materials 0.000 title claims abstract description 64
- 239000000835 fiber Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 47
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 11
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 9
- 239000011701 zinc Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 12
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- 238000001523 electrospinning Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- DXODQEHVNYHGGW-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctyl-tris(trifluoromethoxy)silane Chemical group FC(F)(F)O[Si](OC(F)(F)F)(OC(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F DXODQEHVNYHGGW-UHFFFAOYSA-N 0.000 claims description 7
- 229940057499 anhydrous zinc acetate Drugs 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims description 7
- 230000000845 anti-microbial effect Effects 0.000 claims description 5
- 229940089951 perfluorooctyl triethoxysilane Drugs 0.000 claims description 5
- 239000004599 antimicrobial Substances 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 21
- 229910052731 fluorine Inorganic materials 0.000 abstract description 2
- 239000011737 fluorine Substances 0.000 abstract description 2
- 239000012784 inorganic fiber Substances 0.000 abstract description 2
- 230000002045 lasting effect Effects 0.000 abstract description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 230000003115 biocidal effect Effects 0.000 abstract 1
- 239000002121 nanofiber Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- 239000006916 nutrient agar Substances 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 208000035143 Bacterial infection Diseases 0.000 description 1
- 241000192125 Firmicutes Species 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 1
- 230000014599 transmission of virus Effects 0.000 description 1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic System; Zincates; Cadmates
-
- 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
- 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
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
Abstract
The invention belongs to the technical field of inorganic fiber antibiosis, and provides ZnO-loaded fluorinated SiO 2 Fiber, and a preparation method and application thereof. The preparation method comprises the following steps: s1, mixing tetraethoxysilane, hydrochloric acid solution, ethanol and water, and reacting to obtain SiO 2 Sol; s2, siO 2 Mixing the sol and fluoride, reacting, and obtaining fluorinated SiO by electrostatic spinning technology after the reaction is finished 2 Fibers; s3, fluorinating SiO 2 Adding the fiber into a Zn precursor solution for hydrothermal reaction to obtain ZnO-loaded fluorinated SiO 2 And (3) fibers. The ZnO-loaded fluorinated SiO prepared by the invention 2 The fiber contains double active components of ZnO and fluorine, so that the ZnO-loaded fluorinated SiO 2 The antibacterial performance of the fiber is longer-acting and lasting.
Description
Technical Field
The invention relates to inorganic fiber resistsThe technical field of bacteria, in particular to ZnO-loaded fluorinated SiO 2 Fiber and a preparation method and application thereof.
Background
Currently, diseases caused by bacterial infections or viral transmission face increasingly serious safety and health threats to humans, which afflict us in different forms, one after another, resulting in huge losses of human life and property. The wide use of antibacterial materials has made people's desire for health and safety awareness stronger and stronger.
In the research of inorganic antibacterial nano-fiber, siO 2 Nanofibers have many unique properties such as large specific surface area, low thermal conductivity, chemical inertness, good biocompatibility, safety, non-toxicity, and SiO 2 The microporous environment in the nanofibers can provide support for the slow release of the antimicrobial composition. SiO 2 2 The excellent performance of the nano-fiber enables the nano-fiber to be widely applied to the aspects of sensors, catalysts, conductive fibers, biomedicine and the like. Furthermore, siO 2 The nano fiber does not show any inherent Raman characteristic peak in surface enhanced Raman scattering detection, so that the nano fiber becomes an ideal matrix material, namely SiO 2 The biocompatibility of nanofibers makes them particularly attractive in the biomedical field, especially in wound dressings, medical hygiene, tissue engineering and even food packaging. However, pure SiO 2 The nanofibers have a pronounced hydrophilicity, which is difficult to achieve with a hydrophilic surface anti-adhesion properties for bacteria. Therefore, a hydrophobic substance must be selected to chemically modify the surface of the substrate, so as to obtain a hydrophobic interface.
Among various inorganic antibacterial agents, nano ZnO has been verified to have good antibacterial activity against gram-positive bacteria and gram-negative bacteria. In addition, znO is widely used in the fields of food, cosmetics, and medicine because of its safety and biocompatibility. However, no mature theoretical research and practical application exists so far, so that ZnO and SiO 2 The nano-fiber is simultaneously applied to the antibacterial material.
Therefore, how to treat pure SiO 2 Modifying nano-fiber and modifying SiO 2 The simultaneous application of nanofibers and ZnO in antimicrobial materials has become a problem that those skilled in the art need to solve.
Disclosure of Invention
In view of the above, the present invention provides a fluorinated SiO supported with ZnO 2 The fiber, the preparation method and the application thereof aim to improve the technical problems of poor antibacterial effect and short antibacterial aging of the existing inorganic antibacterial agent.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides ZnO-loaded fluorinated SiO 2 A method of making a fiber comprising the steps of:
s1, mixing tetraethoxysilane, hydrochloric acid solution, ethanol and water, and reacting to obtain SiO 2 Sol;
S2、SiO 2 mixing the sol and fluoride, reacting, and obtaining fluorinated SiO by electrostatic spinning technology after the reaction is finished 2 Fibers;
s3, fluorinating SiO 2 Adding the fiber into a Zn precursor solution for hydrothermal reaction to obtain ZnO-loaded fluorinated SiO 2 And (3) fibers.
Further, in the step S1, the volume ratio of the tetraethoxysilane to the hydrochloric acid solution to the ethanol to the water is 60 to 80:6 to 8:20 to 27:12 to 20.
Further, in the step S1, the mass concentration of the hydrochloric acid solution is 1-5%; the reaction temperature is 60-90 ℃, and the reaction time is 2-4 h; the reaction is carried out under the condition of stirring, and the rotating speed of the stirring is 300-800 rpm.
Further, in the step S2, the fluoride is perfluorooctyl trimethoxy silane and/or 1H, 2H-perfluorooctyl triethoxy silane; the reaction time is 0.1-0.5 h;
the SiO 2 The mass ratio of the sol to the fluoride is 1-5: 1.
further, in the step S2, the conditions of the electrospinning technique are as follows: the anode voltage is 10-30 kV, the working distance is 10-20 cm, and the solution flow rate is 1-5 mL/h.
Further, in the step S3, the temperature of the hydrothermal reaction is 120-180 ℃, and the time of the hydrothermal reaction is 10-20 h.
Further, in the step S3, the Zn source in the Zn precursor solution is anhydrous zinc acetate and/or anhydrous zinc nitrate; the mass concentration of the Zn precursor solution is 0.1-0.5%.
Further, in the step S3, siO is fluorinated 2 The mass volume ratio of the fiber to the Zn precursor solution is 1g: 1-5 mL.
The invention provides ZnO-loaded fluorinated SiO prepared by the preparation method 2 And (3) fibers.
The invention also provides the ZnO-loaded fluorinated SiO 2 Use of fibres in the manufacture of an antimicrobial fabric.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
1. in the invention, the fluoride enables the fiber to have stronger hydrophobicity, thereby endowing the fiber with remarkable antibacterial adhesion activity; the coexistence of double active components ZnO and fluorine ensures that the ZnO-loaded fluorinated SiO prepared by the invention 2 The antibacterial performance of the fiber is longer-acting and lasting;
2. the invention has no addition of any high molecular material in the preparation process, ensures the characteristics of the pure inorganic nano-fiber and ensures that the pure inorganic nano-fiber has good biocompatibility;
3. ZnO-loaded fluorinated SiO prepared by the invention 2 The fiber can achieve the dual antibacterial effect of rejection/contact from the antibacterial mechanism, and has more obvious antibacterial effect than the antibacterial effect of a pure rejection type or contact type antibacterial material.
Drawings
FIG. 1 shows ZnO-loaded fluorinated SiO prepared in example 1 of the present invention 2 SEM image of the fibers.
Detailed Description
The invention provides ZnO-loaded fluorinated SiO 2 A method of making a fiber comprising the steps of:
s1, mixing ethyl orthosilicate, hydrochloric acid solution, ethanol and water, and then carrying out reverse reactionSiO should be obtained 2 Sol;
S2、SiO 2 mixing the sol and fluoride, reacting, and obtaining fluorinated SiO by electrostatic spinning technology after the reaction is finished 2 Fibers;
s3, fluorinating SiO 2 Adding the fiber into a Zn precursor solution for hydrothermal reaction to obtain fluorinated SiO loaded with ZnO 2 A fiber.
In the invention, in the step S1, the volume ratio of the ethyl orthosilicate, the hydrochloric acid solution, the ethanol and the water is 60-80: 6 to 8:20 to 27:12 to 20, preferably 62 to 77: 6.5-7.5: 22 to 26:13 to 17, more preferably 66 to 72:7:23 to 25:14 to 16.
In the present invention, in the step S1, the mass concentration of the hydrochloric acid solution is 1 to 5%, preferably 2 to 4%, and more preferably 3%; the reaction temperature is 60-90 ℃, preferably 65-85 ℃, and more preferably 70-80 ℃; the reaction time is 2-4 h, preferably 2.5-3.5 h, and more preferably 3h; the reaction is carried out under stirring conditions at a rotation speed of 300 to 800rpm, preferably 400 to 700rpm, and more preferably 500 to 600rpm.
In the present invention, in the step S2, the fluoride is perfluorooctyltrimethoxysilane and/or 1h, 2h-perfluorooctyltriethoxysilane, preferably perfluorooctyltrimethoxysilane; the reaction time is 0.1-0.5 h, preferably 0.2-0.4 h, and further preferably 0.3h; the reaction is carried out at room temperature; the SiO 2 The mass ratio of the sol to the fluoride is 1-5: 1.
in the present invention, in the step S2, the conditions of the electrospinning technique are: the voltage of the positive electrode is 10-30 kV, preferably 15-25 kV, and more preferably 20kV; the working distance is 10-20 cm, preferably 12-18 cm, and more preferably 14-16 cm; the flow rate of the solution is 1 to 5mL/h, preferably 2 to 4mL/h, and more preferably 3mL/h.
In the present invention, in the step S3, the temperature of the hydrothermal reaction is 120 to 180 ℃, preferably 130 to 160 ℃, and more preferably 140 to 150 ℃; the hydrothermal reaction time is 10 to 20 hours, preferably 12 to 18 hours, and more preferably 14 to 16 hours.
In the present invention, in step S3, the Zn source in the Zn precursor solution is anhydrous zinc acetate and/or anhydrous zinc nitrate, preferably anhydrous zinc acetate; the mass concentration of the Zn precursor solution is 0.1 to 0.5%, preferably 0.2 to 0.4%, and more preferably 0.3%.
In the present invention, in the step S3, siO is fluorinated 2 The mass volume ratio of the fiber to the Zn precursor solution is 1g: 1-5 mL.
The invention provides ZnO-loaded fluorinated SiO prepared by the preparation method 2 And (3) fibers.
The invention also provides the ZnO-loaded fluorinated SiO 2 Use of fibres in the manufacture of an antimicrobial fabric.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
63 parts of tetraethoxysilane, 6.7 parts of HCl with a mass concentration of 1%, 24 parts of ethanol and 14 parts of water were mixed and added to the reaction system, and stirred at 65 ℃ and 450rpm for 2.5 hours to obtain SiO 2 Sol;
mixing SiO 2 The mass ratio of the sol to the perfluorooctyl trimethoxy silane is 3:1, stirring for 0.1h at room temperature, and carrying out electrostatic spinning to obtain fluorinated SiO 2 A fiber, wherein the electrospinning conditions are: the voltage of the positive electrode is 20kV, the working distance is 15cm, and the flow rate of the solution is 3mL/h;
preparing Zn precursor solution with mass concentration of 0.1% by using anhydrous zinc acetate, and fluorinating SiO 2 The mass volume ratio of the fiber is 1g:1mL of the solution is added into a Zn precursor solution, and the hydrothermal reaction is carried out for 14h at the temperature of 125 ℃ to obtain ZnO-loaded fluorinated SiO 2 A fiber.
FIG. 1 shows the fluorination of the ZnO-loaded material prepared in this exampleSiO 2 SEM image of fiber, from FIG. 1, it is clear that ZnO nanoparticles were successfully supported on fluorinated SiO 2 The surface of the fiber.
Example 2
Mixing 66 parts of tetraethoxysilane, 7 parts of HCl with a mass concentration of 2%, 22 parts of ethanol and 15 parts of water, adding to the reaction system, and stirring at 70 ℃ and 500rpm for 3 hours to obtain SiO 2 Sol;
mixing SiO 2 The sol and 1H, 2H-perfluorooctyltriethoxysilane in a mass ratio of 1:1, stirring for 0.2h at room temperature, and carrying out electrostatic spinning to obtain fluorinated SiO 2 A fiber, wherein the conditions of electrospinning are: the voltage of the positive electrode is 22kV, the working distance is 14cm, and the flow rate of the solution is 3mL/h;
preparing Zn precursor solution with mass concentration of 0.2% by using anhydrous zinc acetate, and fluorinating SiO 2 The mass volume ratio of the fiber is 1g:2mL of the solution is added into a Zn precursor solution, and the hydrothermal reaction is carried out for 12 hours at the temperature of 130 ℃ to obtain ZnO-loaded fluorinated SiO 2 A fiber.
Example 3
68 parts of tetraethoxysilane, 8 parts of HCl with a mass concentration of 3%, 25 parts of ethanol and 16 parts of water were mixed and added to a reaction system, and stirred at 75 ℃ and 600rpm for 3 hours to obtain SiO 2 Sol;
mixing SiO 2 The mass ratio of the sol to the perfluorooctyl trimethoxy silane is 2:1, stirring for 0.3h at room temperature, and carrying out electrostatic spinning to obtain fluorinated SiO 2 A fiber, wherein the electrospinning conditions are: the voltage of the positive electrode is 25kV, the working distance is 16cm, and the flow rate of the solution is 3mL/h;
preparing Zn precursor solution with mass concentration of 0.3% by using anhydrous zinc acetate, and fluorinating SiO 2 The mass volume ratio of the fiber is 1g: adding 3mL of the solution into a Zn precursor solution, and carrying out hydrothermal reaction for 13h at the temperature of 140 ℃ to obtain ZnO-loaded fluorinated SiO 2 A fiber.
Example 4
75 parts of ethyl orthosilicate, 6 parts of HCl (4% by mass), 26 parts of ethanol and 18 parts of water were mixed and added to the reaction system, and the mixture was stirred at 80 ℃ and 650rpmStirring for 3 hours under the condition to obtain SiO 2 Sol;
mixing SiO 2 The mass ratio of the sol to 1H, 2H-perfluorooctyltriethoxysilane is 4:1, stirring for 0.4h at room temperature, and carrying out electrostatic spinning to obtain fluorinated SiO 2 A fiber, wherein the electrospinning conditions are: the voltage of the positive electrode is 15kV, the working distance is 12cm, and the flow rate of the solution is 4mL/h;
preparing Zn precursor solution with mass concentration of 0.4% by using anhydrous zinc nitrate, and fluorinating SiO 2 The mass volume ratio of the fiber is 1g:4mL of the solution is added into a Zn precursor solution, and the hydrothermal reaction is carried out for 16h at the temperature of 150 ℃ to obtain fluorinated SiO supported ZnO 2 And (3) fibers.
Example 5
80 parts of ethyl orthosilicate, 6 parts of HCl with a mass concentration of 5%, 20 parts of ethanol and 20 parts of water are mixed and added into a reaction system, and stirred for 4 hours under the stirring conditions of 90 ℃ and 400rpm to obtain SiO 2 Sol;
mixing SiO 2 The mass ratio of the sol to the perfluorooctyl trimethoxy silane is 5:1, stirring for 0.5h at room temperature, and carrying out electrostatic spinning to obtain fluorinated SiO 2 A fiber, wherein the electrospinning conditions are: the voltage of the positive electrode is 20kV, the working distance is 15cm, and the flow rate of the solution is 5mL/h;
preparing Zn precursor solution with mass concentration of 0.5% by using anhydrous zinc nitrate, and fluorinating SiO 2 The mass volume ratio of the fiber is 1g:5mL of the solution is added into a Zn precursor solution, and the hydrothermal reaction is carried out for 10 hours at the temperature of 180 ℃ to obtain ZnO-loaded fluorinated SiO 2 A fiber.
Performance testing
The ZnO-loaded fluorinated SiO prepared by the invention 2 The antibacterial performance of the fiber is tested, and the specific test steps are as follows: the ZnO-loaded fluorinated SiO prepared in examples 1 to 5 was applied to 7 identical nutrient agar media 2 Fibre, ordinary SiO 2 Fibers and fluorinated SiO 2 Respectively coating the fibers on nutrient agar culture medium, culturing Escherichia coli and Staphylococcus aureus by placing 7 nutrient agar culture media in the same environment, and verifying different SiO by plate counting method 2 The antibacterial effect of the fibers is shown in table 1.
TABLE 1 different SiO 2 Antibacterial effect of fiber
| Sample (I) | Antibacterial rate (Escherichia coli) | Antibacterial rate (Staphylococcus aureus) |
| Example 1 | 100％ | 100％ |
| Example 2 | 100％ | 100％ |
| Example 3 | 100％ | 100％ |
| Example 4 | 100％ | 100％ |
| Example 5 | 100％ | 100％ |
| Ordinary SiO 2 Fiber | 3％ | 2％ |
| Fluorinated SiO 2 Fiber | 65％ | 63％ |
From Table 1, it can be seen that the ZnO-loaded fluorinated SiO prepared by the present invention 2 The antibacterial rate of the fiber to escherichia coli and staphylococcus aureus is high, which shows that the ZnO-loaded fluorinated SiO is 2 The fiber has excellent broad-spectrum antibacterial activity.
In the present specification, the embodiments are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. ZnO-loaded fluorinated SiO 2 The preparation method of the fiber is characterized by comprising the following steps:
s1, mixing ethyl orthosilicate, hydrochloric acid solution, ethanol and water, and reacting to obtain SiO 2 Sol;
S2、SiO 2 mixing the sol and fluoride, reacting, and obtaining fluorinated SiO by electrostatic spinning technology after the reaction is finished 2 Fibers;
s3, fluorinating SiO 2 Adding the fiber into a Zn precursor solution for hydrothermal reaction to obtain ZnO-loaded fluorinated SiO 2 And (3) fibers.
2. The preparation method according to claim 1, wherein in the step S1, the volume ratio of the tetraethoxysilane to the hydrochloric acid solution to the ethanol to the water is 60 to 80:6 to 8:20 to 27:12 to 20.
3. The preparation method according to claim 2, wherein in the step S1, the mass concentration of the hydrochloric acid solution is 1 to 5%; the reaction temperature is 60-90 ℃, and the reaction time is 2-4 h; the reaction is carried out under the condition of stirring, and the rotating speed of the stirring is 300-800 rpm.
4. The production method according to any one of claims 1 to 3, wherein in the step S2, the fluoride is perfluorooctyltrimethoxysilane and/or 1H, 2H-perfluorooctyltriethoxysilane; the reaction time is 0.1-0.5 h;
the SiO 2 The mass ratio of the sol to the fluoride is 1-5: 1.
5. the method according to claim 4, wherein in step S2, the conditions of the electrospinning technique are as follows: the voltage of the positive electrode is 10-30 kV, the working distance is 10-20 cm, and the flow rate of the solution is 1-5 mL/h.
6. The method according to claim 1 or 5, wherein the hydrothermal reaction is carried out at 120 to 180 ℃ for 10 to 20 hours in step S3.
7. The method according to claim 6, wherein in step S3, the Zn source in the Zn precursor solution is anhydrous zinc acetate and/or anhydrous zinc nitrate; the mass concentration of the Zn precursor solution is 0.1-0.5%.
8. The production method according to claim 1, 5 or 7, wherein in the step S3, fluorinated SiO 2 The mass volume ratio of the fiber to the Zn precursor solution is 1g:1～5mL。
9. ZnO-supporting fluorinated SiO solid prepared by the process according to any one of claims 1 to 8 2 And (3) fibers.
10. The ZnO-supported fluorinated SiO of claim 9 2 Use of fibres in the manufacture of an antimicrobial fabric.
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| CN112626641A (en) * | 2020-12-10 | 2021-04-09 | 新疆理工学院 | Method for preparing fluffy flexible three-dimensional silicon dioxide nano-fibers in one step by template-free method |
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| CN101481855A (en) * | 2008-11-27 | 2009-07-15 | 江南大学 | Preparation of silicon dioxide / polyvinylidene fluoride composite nano fiber film |
| CN102013516A (en) * | 2010-10-22 | 2011-04-13 | 浙江大学 | Porous fiber gel polymer electrolyte and preparation method thereof |
| CN102652903A (en) * | 2012-05-03 | 2012-09-05 | 东华大学 | Preparation method of high temperature resistant silicon dioxide nanometer fiber filtering membrane |
| CN103820945A (en) * | 2014-03-12 | 2014-05-28 | 东华大学 | Preparation method of organic/inorganic hybridization nano super-hydrophobic fiber film |
| CN108797094A (en) * | 2018-06-11 | 2018-11-13 | 成都新柯力化工科技有限公司 | A kind of composite membrane and preparation method for flexible piezoelectric material |
| CN112626641A (en) * | 2020-12-10 | 2021-04-09 | 新疆理工学院 | Method for preparing fluffy flexible three-dimensional silicon dioxide nano-fibers in one step by template-free method |
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| CN116377606A (en) * | 2023-04-25 | 2023-07-04 | 武汉纺织大学 | Spiral antibacterial nanofiber as well as preparation method and application thereof |
| CN116377606B (en) * | 2023-04-25 | 2024-03-22 | 武汉纺织大学 | Spiral antibacterial nanofiber as well as preparation method and application thereof |
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