CN114668850A - Preparation method of capacitance antibacterial material - Google Patents
Preparation method of capacitance antibacterial material Download PDFInfo
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- CN114668850A CN114668850A CN202210267804.2A CN202210267804A CN114668850A CN 114668850 A CN114668850 A CN 114668850A CN 202210267804 A CN202210267804 A CN 202210267804A CN 114668850 A CN114668850 A CN 114668850A
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- 239000000463 material Substances 0.000 title claims abstract description 151
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 128
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 104
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 104
- 239000004744 fabric Substances 0.000 claims abstract description 104
- 239000000243 solution Substances 0.000 claims abstract description 55
- 238000000137 annealing Methods 0.000 claims abstract description 54
- 239000002243 precursor Substances 0.000 claims abstract description 52
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 51
- 239000010935 stainless steel Substances 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 31
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007864 aqueous solution Substances 0.000 claims abstract description 30
- 239000004202 carbamide Substances 0.000 claims abstract description 30
- 239000008367 deionised water Substances 0.000 claims abstract description 26
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 241000894006 Bacteria Species 0.000 claims abstract description 19
- 150000001868 cobalt Chemical class 0.000 claims abstract description 10
- 150000004673 fluoride salts Chemical class 0.000 claims abstract description 10
- 239000003990 capacitor Substances 0.000 claims abstract description 5
- 230000009881 electrostatic interaction Effects 0.000 claims abstract description 5
- 230000005540 biological transmission Effects 0.000 claims abstract description 4
- 210000000170 cell membrane Anatomy 0.000 claims abstract description 3
- 230000035755 proliferation Effects 0.000 claims abstract description 3
- 239000004809 Teflon Substances 0.000 claims abstract 2
- 229920006362 Teflon® Polymers 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 106
- 238000001035 drying Methods 0.000 claims description 58
- 239000002070 nanowire Substances 0.000 claims description 54
- 238000005406 washing Methods 0.000 claims description 50
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 25
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 24
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 20
- 230000035484 reaction time Effects 0.000 claims description 7
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 1
- 239000011572 manganese Substances 0.000 abstract description 17
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052748 manganese Inorganic materials 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 description 47
- 238000010438 heat treatment Methods 0.000 description 47
- 230000000052 comparative effect Effects 0.000 description 12
- 210000004027 cell Anatomy 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
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- 239000000725 suspension Substances 0.000 description 3
- 206010059866 Drug resistance Diseases 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
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- 238000002835 absorbance Methods 0.000 description 1
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- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BQRGNLJZBFXNCZ-UHFFFAOYSA-N calcein am Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC(CN(CC(=O)OCOC(C)=O)CC(=O)OCOC(C)=O)=C(OC(C)=O)C=C1OC1=C2C=C(CN(CC(=O)OCOC(C)=O)CC(=O)OCOC(=O)C)C(OC(C)=O)=C1 BQRGNLJZBFXNCZ-UHFFFAOYSA-N 0.000 description 1
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- 238000011534 incubation Methods 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/02—Inorganic compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K33/00—Medicinal preparations containing inorganic active ingredients
- A61K33/24—Heavy metals; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P17/00—Drugs for dermatological disorders
- A61P17/02—Drugs for dermatological disorders for treating wounds, ulcers, burns, scars, keloids, or the like
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/04—Antibacterial agents
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- Public Health (AREA)
- Veterinary Medicine (AREA)
- Medicinal Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Epidemiology (AREA)
- Organic Chemistry (AREA)
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- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
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Abstract
The invention provides a preparation method of a capacitance antibacterial material, which comprises the steps of sequentially dissolving cobalt salt, fluoride salt and urea with certain concentration in deionized water to obtain a precursor solution; then putting the precursor solution and carbon cloth into a Teflon lining stainless steel autoclave, and reacting in an oven; and annealing the sample, and then placing the sample in a potassium permanganate aqueous solution for reaction. The invention takes the carbon cloth with flexible three-dimensional network structure and high conductivity as the material carrier, which not only can improve the electron transmission rate and capacitance performance of the material and inhibit the cobaltosic oxide material from agglomerating, but also ensures that the good flexibility and biocompatibility of the materialThe application range of the material is enlarged; the manganese doping of the invention can further improve the charge transport and activity of cobaltosic oxide, enhance the electrostatic interaction between the capacitor material and bacteria, improve the electron transport capability, destroy the cell membrane of the bacteria, thereby inhibiting the proliferation of the bacteria. The antibacterial activity is obviously improved. The number of colonies was only 100.5CFUmL‑1。
Description
Technical Field
The invention relates to the technical field of antibacterial materials, in particular to a preparation method of a capacitive antibacterial material.
Background
In the aspect of the problem of bacterial infection of various wounds, the current clinic mainly depends on antibiotics for treatment, but the long-term use of antibiotics can gradually enhance the drug resistance of bacteria, and meanwhile, the spectrum of drug-resistant bacteria is continuously expanded, so that the difficulty of clinical treatment and antibiotic research is gradually increased. Fortunately, under the efforts of many researchers, a series of novel antibacterial materials capable of overcoming the conventional antibiotic short plates have been developed, such as silver-based antibacterial materials having the advantages of excellent antibacterial ability, long-term efficacy, and being not easy to generate drug resistance, etc., and photocatalytic antibacterial materials (mainly including TiO2 and ZnO) having the advantages of low cost, good antibacterial property, high biocompatibility, etc. Unfortunately, these antibacterial materials also have some considerable disadvantages, such as higher cost, stronger toxicity, easy oxidation to cause skin discoloration, etc. of silver-based antibacterial materials, and the antibacterial performance of photocatalytic antibacterial materials is still to be improved. Based on the above situation, there is still a need to develop an antibacterial material that satisfies the conditions of low cost, high biocompatibility, no toxicity, high antibacterial activity, etc.
In recent years, in a lot of researches, people in related fields find that bacteria with negative charges on the surface can destroy the cell membrane structure through electrostatic interaction with an antibacterial material with positive charges, and further achieve the sterilization and antibacterial effects. However, some of the currently developed antibacterial materials have a limited amount of surface charges, and are rapidly neutralized after electrostatic interaction with bacteria, so that the antibacterial materials are ineffective and cannot meet the clinical long-term antibacterial requirement. Therefore, it is of great significance to develop a capacitive antibacterial material which can store a large amount of positive charges on the surface of the material by charging, has low cost, no toxicity and good biocompatibility.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the preparation method of the capacitance antibacterial material which is environment-friendly, low in cost, high in antibacterial rate, long in aging and good in biocompatibility.
The technical scheme of the invention is as follows: a preparation method of a capacitance antibacterial material comprises the following steps:
s1), sequentially dissolving cobalt salt, fluoride salt and urea with certain concentration in deionized water, and uniformly stirring at normal temperature to obtain a precursor solution;
s2), placing the precursor solution and the pretreated carbon cloth in a Teflon-lined stainless steel autoclave, reacting in a drying oven at a certain temperature for a certain time, washing the obtained sample for three times by using ethanol after the reaction is finished, and drying in the drying oven;
s3), annealing the sample obtained in the step S2) in air at a certain temperature for a certain time to obtain the cobaltosic oxide nanowire material growing on the carbon cloth;
s4), completely placing the cobaltosic oxide nanowire material obtained in the step S3) into a Teflon-lined stainless steel autoclave containing potassium permanganate aqueous solution with certain concentration, keeping the temperature for a certain time, washing the sample for three times by using ethanol, and drying the sample in an oven to obtain the manganese-doped cobaltosic oxide nanowire material.
Preferably, in step S1), the cobalt salt is one or a combination of cobalt chloride, cobalt acetate, cobalt sulfate and cobalt nitrate.
More preferably, in step S1), the cobalt salt is cobalt chloride.
Preferably, in the step S1), the concentration of the cobalt salt is 0.05-0.5 mol/L.
More preferably, in step S1), the concentration of the cobalt salt is 0.15 mol/L.
Preferably, in step S1), the fluoride salt is one or a combination of ammonium fluoride, sodium fluoride, potassium fluoride or aluminum fluoride.
More preferably, in step S1), the fluoride salt is ammonium fluoride.
Preferably, in the step S1), the concentration of the fluoride salt is 0.05-0.5 mol/L.
More preferably, in step S1), the fluoride salt concentration is 0.28 mol/L.
Preferably, in the step S1), the concentration of the urea is 0.2-2 mol/L.
More preferably, in step S1), the urea concentration is 0.7 mol/L.
Preferably, in step S2), the carbon cloth is pre-treated by ultrasonic cleaning with 3mol/L diluted hydrochloric acid and ethanol for 10min, wherein the ultrasonic power is 320W.
Preferably, in the step S2), the temperature of the oven reaction is 80 to 180 ℃, and the reaction time is 2 to 10 hours.
More preferably, in step S2), the temperature of the oven reaction is 120 ℃, and the reaction time is 6 h.
Preferably, in the steps S2) and S4), the drying temperature in the oven is 60 ℃, and the drying time is 12 h.
Preferably, in step S3), the annealing process includes the following specific operations: raising the temperature to 100-500 ℃ at a heating rate of 5 ℃/min, then preserving the heat for 0.5-5 h, and finally reducing the temperature to room temperature at a cooling rate of 5 ℃/min.
More preferably, in step S3), the annealing temperature is 350 ℃ and the annealing time is 2 h.
Preferably, in the step S4), the concentration of the potassium permanganate aqueous solution is 0.01-1 mol/L.
More preferably, in step S4), the concentration of the potassium permanganate aqueous solution is 0.03 mol/L.
Preferably, in the step S4), the reaction temperature is 100-200 ℃ and the reaction time is 0.5-3 h.
More preferably, in step S4), the reaction temperature is 160 ℃ and the reaction time is 1 h.
The invention has the beneficial effects that:
1. the manganese-doped cobaltosic oxide capacitance antibacterial material obtained through the hydrothermal reaction which is simple and easy to operate has the advantages of long aging time, good biocompatibility, super-strong antibacterial activity and the like, and the carbon cloth with a flexible three-dimensional network structure and high conductivity is used as a material carrier, so that the electronic transmission rate and the capacitance performance of the material can be improved, the cobaltosic oxide material is inhibited from agglomerating, and the application range of the material is enlarged due to the good flexibility and the biocompatibility of the material;
2. The manganese doping of the invention can further improve the charge transport and activity of cobaltosic oxide, enhance the electrostatic interaction between the capacitor material and bacteria, improve the electron transport capability, destroy the cell membrane of the bacteria, thereby inhibiting the proliferation of the bacteria.
Drawings
FIG. 1 is an XRD pattern of C-Co and C-Co/Mn materials prepared in comparative example 1 and example 1, respectively, according to the present invention;
FIG. 2 is an SEM image of a material according to an example of the present invention, wherein (a) and (b) are SEM images of C-Co and C-Co/Mn materials prepared in comparative example 1 and example 1, respectively, and (C) is an EDS image of the C-Co/Mn material;
FIG. 3 is a graph showing the antibacterial effect of the materials of the examples according to the present invention, wherein (a) (b) shows the antibacterial effect of the C-Co prepared in comparative example 1 and the antibacterial effect of the C-Co/Mn antibacterial material prepared in example 1 on Escherichia coli, and (C) shows the number of colonies of the C-Co and C-Co/Mn antibacterial materials after they act on Escherichia coli.
FIG. 4 is a graph showing cell death after the material according to the example of the present invention is applied, in which (a) (b) are cell death after the C-Co prepared in comparative example 1 and the C-Co/Mn antibacterial material prepared in example 1 are applied, respectively.
Detailed Description
The following further describes embodiments of the present invention with reference to the accompanying drawings:
Example 1
The embodiment provides a preparation method of a capacitance antibacterial material, which comprises the following steps:
s1), sequentially dissolving 0.15mol/L cobalt nitrate, 0.28mol/L ammonium fluoride and 0.7mol/L urea in 40mL deionized water, and uniformly stirring at normal temperature to obtain a precursor solution;
s2), placing the precursor solution and the pretreated carbon cloth in a 50mL Teflon-lined stainless steel autoclave, reacting for 6h in a 120 ℃ oven, washing the obtained sample for three times by using ethanol after the reaction is finished, and drying in a 60 ℃ oven;
s3), and annealing the sample obtained in S2) in air at 350 ℃ for 2 h. Wherein the annealing treatment is specifically carried out by heating the carbon cloth to 350 ℃ at a heating rate of 5 ℃/min, then preserving the heat for 2h, and finally cooling the carbon cloth to room temperature at a cooling rate of 5 ℃/min to obtain the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth;
s4), completely placing the C-Co sample obtained in the step S3) into a 50mL Teflon-lined stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, washing the sample with ethanol for three times, and drying the sample in an oven at 60 ℃ for 12h to obtain the manganese-doped cobaltosic oxide nanowire material (marked as C-Co/Mn-1).
Example 2
The embodiment provides a preparation method of a capacitive antibacterial material, which comprises the following steps:
s1), sequentially dissolving 0.15mol/L cobalt nitrate, 0.28mol/L sodium fluoride and 0.7mol/L urea in 40mL deionized water, and uniformly stirring at normal temperature to obtain a precursor solution;
s2), placing the precursor solution and the pretreated carbon cloth in a 50mL Teflon-lined stainless steel autoclave, reacting for 6h in a 120 ℃ oven, washing the obtained sample with ethanol for three times after the reaction is finished, and drying in a 60 ℃ oven;
s3), the sample obtained in S2) was placed in air at 350 ℃ for annealing treatment for 2 h. Wherein the annealing treatment is specifically carried out by heating the carbon cloth to 350 ℃ at a heating rate of 5 ℃/min, then preserving the heat for 2h, and finally cooling the carbon cloth to room temperature at a cooling rate of 5 ℃/min to obtain the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth;
s4), completely placing the C-Co sample obtained in the step S3) into a 50mL Teflon-lined stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, washing the sample with ethanol for three times, and drying the sample in an oven at 60 ℃ for 12h to obtain the manganese-doped cobaltosic oxide nanowire material (marked as C-Co/Mn-2).
Example 3
The embodiment provides a preparation method of a capacitive antibacterial material, which comprises the following steps:
s1), sequentially dissolving 0.15mol/L cobalt sulfate, 0.28mol/L ammonium fluoride and 0.7mol/L urea in 40mL deionized water, and uniformly stirring at normal temperature to obtain a precursor solution;
s2), placing the precursor solution and the pretreated carbon cloth in a 50mL Teflon-lined stainless steel autoclave, reacting for 6h in a 120 ℃ oven, washing the obtained sample for three times by using ethanol after the reaction is finished, and drying in a 60 ℃ oven;
s3), and annealing the sample obtained in S2) in air at 350 ℃ for 2 h. Wherein the annealing treatment is specifically carried out by heating the carbon cloth to 350 ℃ at a heating rate of 5 ℃/min, then preserving the heat for 2h, and finally cooling the carbon cloth to room temperature at a cooling rate of 5 ℃/min to obtain the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth;
s4), completely placing the C-Co sample obtained in the step S3) into a 50mL Teflon-lined stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, washing the sample with ethanol for three times, and drying the sample in an oven at 60 ℃ for 12h to obtain the manganese-doped cobaltosic oxide nanowire material (marked as C-Co/Mn-3).
Example 4
The embodiment provides a preparation method of a capacitance antibacterial material, which comprises the following steps:
s1), sequentially dissolving 0.05mol/L cobalt nitrate, 0.28mol/L ammonium fluoride and 0.7mol/L urea in 40mL deionized water, and uniformly stirring at normal temperature to obtain a precursor solution;
s2), placing the precursor solution and the pretreated carbon cloth in a 50mL Teflon-lined stainless steel autoclave, reacting for 6h in a 120 ℃ oven, washing the obtained sample for three times by using ethanol after the reaction is finished, and drying in a 60 ℃ oven;
s3), and annealing the sample obtained in S2) in air at 350 ℃ for 2 h. Wherein the annealing treatment is specifically carried out by heating the carbon cloth to 350 ℃ at a heating rate of 5 ℃/min, then preserving the heat for 2h, and finally cooling the carbon cloth to room temperature at a cooling rate of 5 ℃/min to obtain the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth;
s4), completely placing the C-Co sample obtained in the step S3) in a 50mL Teflon-lined stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, washing the sample with ethanol for three times, and drying the sample in an oven at 60 ℃ for 12h to obtain the manganese-doped cobaltosic oxide nanowire material (marked as C-Co/Mn-4).
Example 5
The embodiment provides a preparation method of a capacitive antibacterial material, which comprises the following steps:
s1), sequentially dissolving 0.25mol/L cobalt nitrate, 0.28mol/L ammonium fluoride and 0.7mol/L urea in 40mL deionized water, and uniformly stirring at normal temperature to obtain a precursor solution;
s2), placing the precursor solution and the pretreated carbon cloth in a 50mL Teflon-lined stainless steel autoclave, reacting for 6h in a 120 ℃ oven, washing the obtained sample for three times by using ethanol after the reaction is finished, and drying in a 60 ℃ oven;
s3), and annealing the sample obtained in S2) in air at 350 ℃ for 2 h. Wherein the annealing treatment is specifically carried out by heating the carbon cloth to 350 ℃ at a heating rate of 5 ℃/min, then preserving the heat for 2h, and finally cooling the carbon cloth to room temperature at a cooling rate of 5 ℃/min to obtain the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth;
s4), completely placing the C-Co sample obtained in the step S3) into a 50mL Teflon-lined stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, washing the sample with ethanol for three times, and drying the sample in an oven at 60 ℃ for 12h to obtain the manganese-doped cobaltosic oxide nanowire material (marked as C-Co/Mn-5).
Example 6
The embodiment provides a preparation method of a capacitive antibacterial material, which comprises the following steps:
s1), sequentially dissolving 0.15mol/L cobalt nitrate, 0.1mol/L ammonium fluoride and 0.7mol/L urea in 40mL deionized water, and uniformly stirring at normal temperature to obtain a precursor solution;
s2), placing the precursor solution and the pretreated carbon cloth in a 50mL Teflon-lined stainless steel autoclave, reacting for 6h in a 120 ℃ oven, washing the obtained sample for three times by using ethanol after the reaction is finished, and drying in a 60 ℃ oven;
s3), and annealing the sample obtained in S2) in air at 350 ℃ for 2 h. Wherein the annealing treatment is specifically carried out by heating the carbon cloth to 350 ℃ at a heating rate of 5 ℃/min, then preserving the heat for 2h, and finally cooling the carbon cloth to room temperature at a cooling rate of 5 ℃/min to obtain the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth;
s4), completely placing the C-Co sample obtained in the step S3) into a 50mL Teflon-lined stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, washing the sample with ethanol for three times, and drying the sample in an oven at 60 ℃ for 12h to obtain the manganese-doped cobaltosic oxide nanowire material (marked as C-Co/Mn-6).
Example 7
The embodiment provides a preparation method of a capacitive antibacterial material, which comprises the following steps:
s1), sequentially dissolving 0.15mol/L cobalt nitrate, 0.35mol/L ammonium fluoride and 0.7mol/L urea in 40mL deionized water, and uniformly stirring at normal temperature to obtain a precursor solution;
s2), placing the precursor solution and the pretreated carbon cloth in a 50mL Teflon-lined stainless steel autoclave, reacting for 6h in a 120 ℃ oven, washing the obtained sample for three times by using ethanol after the reaction is finished, and drying in a 60 ℃ oven;
s3), the sample obtained in S2) was placed in air at 350 ℃ for annealing treatment for 2 h. Wherein the annealing treatment is specifically carried out by heating the carbon cloth to 350 ℃ at a heating rate of 5 ℃/min, then preserving the heat for 2h, and finally cooling the carbon cloth to room temperature at a cooling rate of 5 ℃/min to obtain the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth;
s4), completely placing the C-Co sample obtained in the step S3) into a 50mL Teflon-lined stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, washing the sample with ethanol for three times, and drying the sample in an oven at 60 ℃ for 12h to obtain the manganese-doped cobaltosic oxide nanowire material (marked as C-Co/Mn-7).
Example 8
The embodiment provides a preparation method of a capacitive antibacterial material, which comprises the following steps:
s1), sequentially dissolving 0.15mol/L cobalt nitrate, 0.28mol/L ammonium fluoride and 0.3mol/L urea in 40mL deionized water, and uniformly stirring at normal temperature to obtain a precursor solution;
s2), placing the precursor solution and the pretreated carbon cloth in a 50mL Teflon-lined stainless steel autoclave, reacting for 6h in a 120 ℃ oven, washing the obtained sample with ethanol for three times after the reaction is finished, and drying in a 60 ℃ oven;
s3), the sample obtained in S2) was placed in air at 350 ℃ for annealing treatment for 2 h. Wherein the annealing treatment is specifically carried out by heating the carbon cloth to 350 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 2h, and finally cooling the carbon cloth to room temperature at a cooling rate of 5 ℃/min to obtain a cobaltosic oxide nanowire material (marked as C-Co) grown on the carbon cloth;
s4), completely placing the C-Co sample obtained in the step S3) into a 50mL Teflon-lined stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, washing the sample with ethanol for three times, and drying the sample in an oven at 60 ℃ for 12h to obtain the manganese-doped cobaltosic oxide nanowire material (marked as C-Co/Mn-8).
Example 9
The embodiment provides a preparation method of a capacitive antibacterial material, which comprises the following steps:
s1), sequentially dissolving 0.15mol/L cobalt nitrate, 0.28mol/L ammonium fluoride and 1.5mol/L urea in 40mL deionized water, and uniformly stirring at normal temperature to obtain a precursor solution;
s2), placing the precursor solution and the pretreated carbon cloth in a 50mL Teflon-lined stainless steel autoclave, reacting for 6h in a 120 ℃ oven, washing the obtained sample with ethanol for three times after the reaction is finished, and drying in a 60 ℃ oven;
s3), the sample obtained in S2) was placed in air at 350 ℃ for annealing treatment for 2 h. Wherein the annealing treatment is specifically carried out by heating the carbon cloth to 350 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 2h, and finally cooling the carbon cloth to room temperature at a cooling rate of 5 ℃/min to obtain a cobaltosic oxide nanowire material (marked as C-Co) grown on the carbon cloth;
s4), completely placing the C-Co sample obtained in the step S3) in a 50mL Teflon-lined stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, washing the sample with ethanol for three times, and drying the sample in an oven at 60 ℃ for 12h to obtain the manganese-doped cobaltosic oxide nanowire material (marked as C-Co/Mn-9).
Example 10
The embodiment provides a preparation method of a capacitive antibacterial material, which comprises the following steps:
s1), sequentially dissolving 0.15mol/L cobalt nitrate, 0.28mol/L ammonium fluoride and 0.7mol/L urea in 40mL deionized water, and uniformly stirring at normal temperature to obtain a precursor solution;
s2), placing the precursor solution and the pretreated carbon cloth in a 50mL Teflon-lined stainless steel autoclave, reacting for 6h in an oven at 80 ℃, washing the obtained sample with ethanol for three times after the reaction is finished, and drying in the oven at 60 ℃;
s3), the sample obtained in S2) was placed in air at 350 ℃ for annealing treatment for 2 h. Wherein the annealing treatment is specifically carried out by heating the carbon cloth to 350 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 2h, and finally cooling the carbon cloth to room temperature at a cooling rate of 5 ℃/min to obtain a cobaltosic oxide nanowire material (marked as C-Co) grown on the carbon cloth;
s4), completely placing the C-Co sample obtained in the step S3) in a 50mL Teflon-lined stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, washing the sample with ethanol for three times, and drying the sample in an oven at 60 ℃ for 12h to obtain the manganese-doped cobaltosic oxide nanowire material (marked as C-Co/Mn-10).
Example 11
The embodiment provides a preparation method of a capacitive antibacterial material, which comprises the following steps:
s1), sequentially dissolving 0.15mol/L cobalt nitrate, 0.28mol/L ammonium fluoride and 0.7mol/L urea in 40mL deionized water, and uniformly stirring at normal temperature to obtain a precursor solution;
s2), placing the precursor solution and the pretreated carbon cloth in a 50mL Teflon-lined stainless steel autoclave, reacting for 6h in a 180 ℃ oven, washing the obtained sample with ethanol for three times after the reaction is finished, and drying in a 60 ℃ oven;
s3), the sample obtained in S2) was placed in air at 350 ℃ for annealing treatment for 2 h. Wherein the annealing treatment is specifically carried out by heating the carbon cloth to 350 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 2h, and finally cooling the carbon cloth to room temperature at a cooling rate of 5 ℃/min to obtain a cobaltosic oxide nanowire material (marked as C-Co) grown on the carbon cloth;
s4), completely placing the C-Co sample obtained in the step S3) into a 50mL Teflon-lined stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, washing the sample with ethanol for three times, and drying the sample in an oven at 60 ℃ for 12h to obtain the manganese-doped cobaltosic oxide nanowire material (marked as C-Co/Mn-11).
Example 12
The embodiment provides a preparation method of a capacitance antibacterial material, which comprises the following steps:
s1), sequentially dissolving 0.15mol/L cobalt nitrate, 0.28mol/L ammonium fluoride and 0.7mol/L urea in 40mL deionized water, and uniformly stirring at normal temperature to obtain a precursor solution;
s2), placing the precursor solution and the pretreated carbon cloth in a 50mL Teflon-lined stainless steel autoclave, reacting for 3h in a 120 ℃ oven, washing the obtained sample for three times by using ethanol after the reaction is finished, and drying in a 60 ℃ oven;
s3), and annealing the sample obtained in S2) in air at 350 ℃ for 2 h. Wherein the annealing treatment is specifically carried out by heating the carbon cloth to 350 ℃ at a heating rate of 5 ℃/min, then preserving the heat for 2h, and finally cooling the carbon cloth to room temperature at a cooling rate of 5 ℃/min to obtain the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth;
s4), completely placing the C-Co sample obtained in the step S3) into a 50mL Teflon-lined stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, washing the sample with ethanol for three times, and drying the sample in an oven at 60 ℃ for 12h to obtain the manganese-doped cobaltosic oxide nanowire material (marked as C-Co/Mn-12).
Example 13
The embodiment provides a preparation method of a capacitance antibacterial material, which comprises the following steps:
s1), sequentially dissolving 0.15mol/L cobalt nitrate, 0.28mol/L ammonium fluoride and 0.7mol/L urea in 40mL deionized water, and uniformly stirring at normal temperature to obtain a precursor solution;
s2), placing the precursor solution and the pretreated carbon cloth in a 50mL Teflon-lined stainless steel autoclave, reacting for 10h in a 120 ℃ oven, washing the obtained sample with ethanol for three times after the reaction is finished, and drying in a 60 ℃ oven;
s3), and annealing the sample obtained in S2) in air at 350 ℃ for 2 h. Wherein the annealing treatment is specifically carried out by heating the carbon cloth to 350 ℃ at a heating rate of 5 ℃/min, then preserving the heat for 2h, and finally cooling the carbon cloth to room temperature at a cooling rate of 5 ℃/min to obtain the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth;
s4), completely placing the C-Co sample obtained in the step S3) into a 50mL Teflon-lined stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, washing the sample with ethanol for three times, and drying the sample in an oven at 60 ℃ for 12h to obtain the manganese-doped cobaltosic oxide nanowire material (marked as C-Co/Mn-13).
Example 14
The embodiment provides a preparation method of a capacitive antibacterial material, which comprises the following steps:
s1), sequentially dissolving 0.15mol/L cobalt nitrate, 0.28mol/L ammonium fluoride and 0.7mol/L urea in 40mL deionized water, and uniformly stirring at normal temperature to obtain a precursor solution;
s2), placing the precursor solution and the pretreated carbon cloth in a 50mL Teflon-lined stainless steel autoclave, reacting for 6h in a 120 ℃ oven, washing the obtained sample for three times by using ethanol after the reaction is finished, and drying in a 60 ℃ oven;
s3), and annealing the sample obtained in S2) in air at 350 ℃ for 2 h. Wherein the annealing treatment is specifically carried out by heating the carbon cloth to 150 ℃ at a heating rate of 5 ℃/min, then preserving the heat for 2h, and finally cooling the carbon cloth to room temperature at a cooling rate of 5 ℃/min to obtain the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth;
s4), completely placing the C-Co sample obtained in the step S3) into a 50mL Teflon-lined stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, washing the sample with ethanol for three times, and drying the sample in an oven at 60 ℃ for 12h to obtain the manganese-doped cobaltosic oxide nanowire material (marked as C-Co/Mn-14).
Example 15
The embodiment provides a preparation method of a capacitive antibacterial material, which comprises the following steps:
s1), sequentially dissolving 0.15mol/L cobalt nitrate, 0.28mol/L ammonium fluoride and 0.7mol/L urea in 40mL deionized water, and uniformly stirring at normal temperature to obtain a precursor solution;
s2), placing the precursor solution and the pretreated carbon cloth in a 50mL Teflon-lined stainless steel autoclave, reacting for 6h in a 120 ℃ oven, washing the obtained sample with ethanol for three times after the reaction is finished, and drying in a 60 ℃ oven;
s3), the sample obtained in S2) was placed in air at 350 ℃ for annealing treatment for 2 h. Wherein the annealing treatment is specifically carried out by heating the carbon cloth to 450 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 2h, and finally cooling the carbon cloth to room temperature at a cooling rate of 5 ℃/min to obtain a cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth;
s4), completely placing the C-Co sample obtained in the step S3) in a 50mL Teflon-lined stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, washing the sample with ethanol for three times, and drying the sample in an oven at 60 ℃ for 12h to obtain the manganese-doped cobaltosic oxide nanowire material (marked as C-Co/Mn-15).
Example 16
The embodiment provides a preparation method of a capacitive antibacterial material, which comprises the following steps:
s1), sequentially dissolving 0.15mol/L cobalt nitrate, 0.28mol/L ammonium fluoride and 0.7mol/L urea in 40mL deionized water, and uniformly stirring at normal temperature to obtain a precursor solution;
s2), placing the precursor solution and the pretreated carbon cloth in a 50mL Teflon-lined stainless steel autoclave, reacting for 6h in a 120 ℃ oven, washing the obtained sample with ethanol for three times after the reaction is finished, and drying in a 60 ℃ oven;
s3), the sample obtained in S2) was placed in air at 350 ℃ for annealing treatment for 2 h. Wherein the annealing treatment is specifically carried out by heating the carbon cloth to 350 ℃ at a heating rate of 5 ℃/min, then preserving the heat for 1h, and finally cooling the carbon cloth to room temperature at a cooling rate of 5 ℃/min to obtain the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth;
s4), completely placing the C-Co sample obtained in the step S3) into a 50mL Teflon-lined stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, washing the sample with ethanol for three times, and drying the sample in an oven at 60 ℃ for 12h to obtain the manganese-doped cobaltosic oxide nanowire material (marked as C-Co/Mn-16).
Example 17
The embodiment provides a preparation method of a capacitance antibacterial material, which comprises the following steps:
s1), sequentially dissolving 0.15mol/L cobalt nitrate, 0.28mol/L ammonium fluoride and 0.7mol/L urea in 40mL deionized water, and uniformly stirring at normal temperature to obtain a precursor solution;
s2), placing the precursor solution and the pretreated carbon cloth in a 50mL Teflon-lined stainless steel autoclave, reacting for 6h in a 120 ℃ oven, washing the obtained sample for three times by using ethanol after the reaction is finished, and drying in a 60 ℃ oven;
s3), and annealing the sample obtained in S2) in air at 350 ℃ for 2 h. Wherein the annealing treatment is specifically carried out by heating the carbon cloth to 350 ℃ at a heating rate of 5 ℃/min, then preserving the heat for 4h, and finally cooling the carbon cloth to room temperature at a cooling rate of 5 ℃/min to obtain the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth;
s4), completely placing the C-Co sample obtained in the step S3) in a 50mL Teflon-lined stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, washing the sample with ethanol for three times, and drying the sample in an oven at 60 ℃ for 12h to obtain the manganese-doped cobaltosic oxide nanowire material (marked as C-Co/Mn-17).
Example 18
The embodiment provides a preparation method of a capacitive antibacterial material, which comprises the following steps:
s1), sequentially dissolving 0.15mol/L cobalt nitrate, 0.28mol/L ammonium fluoride and 0.7mol/L urea in 40mL deionized water, and uniformly stirring at normal temperature to obtain a precursor solution;
s2), placing the precursor solution and the pretreated carbon cloth in a 50mL Teflon-lined stainless steel autoclave, reacting for 6h in a 120 ℃ oven, washing the obtained sample with ethanol for three times after the reaction is finished, and drying in a 60 ℃ oven;
s3), the sample obtained in S2) was placed in air at 350 ℃ for annealing treatment for 2 h. Wherein the annealing treatment is specifically carried out by heating the carbon cloth to 350 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 2h, and finally cooling the carbon cloth to room temperature at a cooling rate of 5 ℃/min to obtain a cobaltosic oxide nanowire material (marked as C-Co) grown on the carbon cloth;
s4), completely placing the C-Co sample obtained in the step S3) in a 50mL Teflon-lined stainless steel autoclave containing 0.005mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, washing the sample with ethanol for three times, and drying the sample in an oven at 60 ℃ for 12h to obtain the manganese-doped cobaltosic oxide nanowire material (marked as C-Co/Mn-18).
Example 19
The embodiment provides a preparation method of a capacitive antibacterial material, which comprises the following steps:
s1), sequentially dissolving 0.15mol/L cobalt nitrate, 0.28mol/L ammonium fluoride and 0.7mol/L urea in 40mL deionized water, and uniformly stirring at normal temperature to obtain a precursor solution;
s2), placing the precursor solution and the pretreated carbon cloth in a 50mL Teflon-lined stainless steel autoclave, reacting for 6h in a 120 ℃ oven, washing the obtained sample for three times by using ethanol after the reaction is finished, and drying in a 60 ℃ oven;
s3), and annealing the sample obtained in S2) in air at 350 ℃ for 2 h. Wherein the annealing treatment is specifically carried out by heating the carbon cloth to 350 ℃ at a heating rate of 5 ℃/min, then preserving the heat for 2h, and finally cooling the carbon cloth to room temperature at a cooling rate of 5 ℃/min to obtain the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth;
s4), completely placing the C-Co sample obtained in the step S3) into a 50mL Teflon-lined stainless steel autoclave containing 0.5mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, washing the sample with ethanol for three times, and drying the sample in an oven at 60 ℃ for 12h to obtain the manganese-doped cobaltosic oxide nanowire material (marked as C-Co/Mn-19).
Example 20
The embodiment provides a preparation method of a capacitive antibacterial material, which comprises the following steps:
s1), sequentially dissolving 0.15mol/L cobalt nitrate, 0.28mol/L ammonium fluoride and 0.7mol/L urea in 40mL deionized water, and uniformly stirring at normal temperature to obtain a precursor solution;
s2), placing the precursor solution and the pretreated carbon cloth in a 50mL Teflon-lined stainless steel autoclave, reacting for 6h in a 120 ℃ oven, washing the obtained sample with ethanol for three times after the reaction is finished, and drying in a 60 ℃ oven;
s3), the sample obtained in S2) was placed in air at 350 ℃ for annealing treatment for 2 h. Wherein the annealing treatment is specifically carried out by heating the carbon cloth to 350 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 2h, and finally cooling the carbon cloth to room temperature at a cooling rate of 5 ℃/min to obtain a cobaltosic oxide nanowire material (marked as C-Co) grown on the carbon cloth;
s4), completely placing the C-Co sample obtained in the step S3) in a 50mL Teflon-lined stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 120 ℃ for 1h, washing the sample with ethanol for three times, and drying the sample in an oven at 60 ℃ for 12h to obtain the manganese-doped cobaltosic oxide nanowire material (marked as C-Co/Mn-20).
Example 21
The embodiment provides a preparation method of a capacitive antibacterial material, which comprises the following steps:
s1), sequentially dissolving 0.15mol/L cobalt nitrate, 0.28mol/L ammonium fluoride and 0.7mol/L urea in 40mL deionized water, and uniformly stirring at normal temperature to obtain a precursor solution;
s2), placing the precursor solution and the pretreated carbon cloth in a 50mL Teflon-lined stainless steel autoclave, reacting for 6h in a 120 ℃ oven, washing the obtained sample with ethanol for three times after the reaction is finished, and drying in a 60 ℃ oven;
s3), the sample obtained in S2) was placed in air at 350 ℃ for annealing treatment for 2 h. Wherein the annealing treatment is specifically carried out by heating the carbon cloth to 350 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 2h, and finally cooling the carbon cloth to room temperature at a cooling rate of 5 ℃/min to obtain a cobaltosic oxide nanowire material (marked as C-Co) grown on the carbon cloth;
s4), completely placing the C-Co sample obtained in the step S3) in a 50mL Teflon-lined stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 200 ℃ for 1h, washing the sample with ethanol for three times, and drying the sample in an oven at 60 ℃ for 12h to obtain the manganese-doped cobaltosic oxide nanowire material (marked as C-Co/Mn-21).
Example 22
The embodiment provides a preparation method of a capacitive antibacterial material, which comprises the following steps:
s1), sequentially dissolving 0.15mol/L cobalt nitrate, 0.28mol/L ammonium fluoride and 0.7mol/L urea in 40mL deionized water, and uniformly stirring at normal temperature to obtain a precursor solution;
s2), placing the precursor solution and the pretreated carbon cloth in a 50mL Teflon-lined stainless steel autoclave, reacting for 6h in a 120 ℃ oven, washing the obtained sample with ethanol for three times after the reaction is finished, and drying in a 60 ℃ oven;
s3), and annealing the sample obtained in S2) in air at 350 ℃ for 2 h. Wherein the annealing treatment is specifically carried out by heating the carbon cloth to 350 ℃ at a heating rate of 5 ℃/min, then preserving the heat for 2h, and finally cooling the carbon cloth to room temperature at a cooling rate of 5 ℃/min to obtain the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth;
s4), completely placing the C-Co sample obtained in the step S3) into a 50mL Teflon-lined stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 0.5h, washing the sample with ethanol for three times, and drying the sample in an oven at 60 ℃ for 12h to obtain the manganese-doped cobaltosic oxide nanowire material (marked as C-Co/Mn-22).
Example 23
The embodiment provides a preparation method of a capacitive antibacterial material, which comprises the following steps:
s1), sequentially dissolving 0.15mol/L cobalt nitrate, 0.28mol/L ammonium fluoride and 0.7mol/L urea in 40mL deionized water, and uniformly stirring at normal temperature to obtain a precursor solution;
s2), placing the precursor solution and the pretreated carbon cloth in a 50mL Teflon-lined stainless steel autoclave, reacting for 6h in a 120 ℃ oven, washing the obtained sample with ethanol for three times after the reaction is finished, and drying in a 60 ℃ oven;
s3), the sample obtained in S2) was placed in air at 350 ℃ for annealing treatment for 2 h. Wherein the annealing treatment is specifically carried out by heating the carbon cloth to 350 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 2h, and finally cooling the carbon cloth to room temperature at a cooling rate of 5 ℃/min to obtain a cobaltosic oxide nanowire material (marked as C-Co) grown on the carbon cloth;
s4), completely placing the C-Co sample obtained in the step S3) in a 50mL Teflon-lined stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 2h, washing the sample with ethanol for three times, and drying the sample in an oven at 60 ℃ for 12h to obtain the manganese-doped cobaltosic oxide nanowire material (marked as C-Co/Mn-23).
Comparative example 1
The comparative example provides a capacitance antibacterial material, and the preparation method thereof is different from that of the example 1 in that: no S4 is present in the preparation process, and the step is marked as C-Co.
Performance test
1. Characterization of the composition
The antibacterial material prepared in example 1 and the surface morphology of the antibacterial material in comparative example 1 are characterized, and the characterization results are shown in fig. 1, fig. 1 is an X-ray diffraction pattern (XRD) of the C-Co and C-Co/Mn-1 samples prepared in comparative example 1 and example 1, and it can be seen that signal peaks of tricobalt tetroxide are shown in XRD patterns of both samples, which proves the successful preparation of tricobalt tetroxide, but no signal peak of manganese is shown in XRD patterns of C-Co/Mn-1, probably because the doping amount is low, the signal peaks are difficult to detect.
2. Morphological and elemental analysis
FIG. 2, wherein (a) and (b) are Scanning Electron Microscope (SEM) images of C-Co and C-Co/Mn-1 samples prepared in comparative example 1 and example 1, respectively. As can be clearly seen from fig. 2(a), the synthesized cobaltosic oxide is a nanowire material grown on a three-dimensional carbon cloth, and has high dispersibility and uniformity. It is worth noting that the doping of the manganese element has no obvious influence on the shape of the cobaltosic oxide, and the manganese element is still a nanowire uniformly grown on the carbon cloth. To demonstrate the successful doping of manganese, this study further conducted elemental analysis of the C-Co/Mn-1 material synthesized in example 1. As shown in fig. 2(c), the sample prepared in example 1 contains three elements of Mn, Co, and O, demonstrating the successful preparation of a manganese-doped tricobalt tetroxide material.
3. Antibacterial experiments
Coli was inoculated in 10mL of LB medium and shaken at 150 rpm for 18h at 37 ℃. Diluted to a concentration of 10 with PBS8CFU mL-1The bacterial suspension of (4). After all instruments and samples were washed with 70% ethanol, the active surface area was 1cm2The C-Co and C-Co/Mn electrodes were placed in the same PBS buffer, charged at 2V for 30min, the charged electrode was wiped with a clean paper towel to absorb the attached solution, and then the electrode was immersed in a solution containing 1mL of a bacterial suspension (10)6CFU mL-1) After 15 and 30min of treatment in a PBS semi-micro plastic test tube, 10 μ L of treated bacteria liquid is taken and the suspension is diluted. Bacteriostatic activity was determined by colony counting, 3 replicates per group. In order to verify the stability of the antibacterial performance of the antibacterial material, the same C-Co and C-Co/Mn electrodes are adopted to carry out a discharge antibacterial effect test on the escherichia coli in the charging process of 7 cycle periods. As shown in FIG. 3, the number of colonies after 60min treatment with the C-Co/Mn antibacterial material was only 100.5CFU mL-1The colony number of the C-Co antibacterial material after 60min treatment is still 105.5CFU mL-1The antibacterial activity of the C-Co/Mn capacitor material is obviously stronger than that of the C-Co capacitor material.
4. Cytotoxicity test
Cells were seeded in 6-well plates (2X 10 per plate) in RPMI 1640 medium containing 10% fetal bovine serum5And culturing for 24 h), and then respectively soaking the charged C-Co and C-Co/Mn electrodes into a cell culture solution for culturing for 24 h. The treated cells were washed with PBS and then MTT reagent was added. After incubation at 37 ℃ for 4h, the crystals were dissolved in DMSO, and the absorbance was read on a microplate reader (Epoch2, Biotek) having a wavelength of 570nm, and the cell viability was qualitatively analyzed by staining with a cell staining kit. Alive fine hairCells were stained with green fluorescent calcein AM and dead cells were stained with red fluorescent PI. Stained cells were imaged under a fluorescent microscope equipped with green and red filters. As shown in FIG. 4, the C-Co and C-Co/Mn capacitive antibacterial materials have no significant cytotoxic activity to cells, i.e., the C-Co and C-Co/Mn capacitive antibacterial materials have no cell toxicity.
TABLE 1 antibacterial Properties of antibacterial materials prepared in examples and comparative examples
As can be seen from table 1, the capacitive antibacterial material prepared by the preparation method of the present invention has excellent antibacterial activity, and in addition, the antibacterial material is non-toxic to human cells and environment-friendly (does not contain heavy metals) compared to the capacitive antibacterial material in the examples, the antibacterial material prepared in example 1 has excellent activity, and when the material acts on bacteria, the survival rate of bacteria can be significantly reduced (the number of colonies is only 10) 0.5CFU mL-1) Meanwhile, the survival rate of the bacteria under the action of the cobaltosic oxide antibacterial material in the comparative example 1 is obviously lower (the colony number is only 10)5.5CFU mL-1)。
As can be seen from the data of other examples, the preparation conditions (such as the type and concentration of cobalt salt, the type and concentration of fluoride salt, the concentration of urea, the concentration of potassium permanganate, the hydrothermal reaction temperature and time of each stage, the temperature and time used in the annealing process, etc.) have a certain influence on the antibacterial activity of the prepared capacitive antibacterial material. After the capacitive antibacterial material prepared in each embodiment of the invention acts on bacteria, the survival rate of the bacteria is obviously reduced compared with that of comparative example 1.
The foregoing embodiments and description have been provided to illustrate the principles and preferred embodiments of the invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The preparation method of the capacitance antibacterial material is characterized by comprising the following steps:
s1), sequentially dissolving cobalt salt with the concentration of 0.05-0.5 mol/L, fluoride salt with the concentration of 0.05-0.5 mol/L and urea with the concentration of 0.2-2 mol/L into deionized water, and uniformly stirring at normal temperature to obtain a precursor solution;
S2), placing the precursor solution and the pretreated carbon cloth in a Teflon lining stainless steel autoclave, reacting for a certain time in a drying oven at a certain temperature, washing the obtained sample with ethanol for three times after the reaction is finished, and drying in the drying oven;
s3), annealing the sample obtained in the step S2) in air at a certain temperature for a certain time to obtain the cobaltosic oxide nanowire material growing on the carbon cloth;
s4), completely placing the cobaltosic oxide nanowire material obtained in the step S3) into a Teflon-lined stainless steel autoclave containing potassium permanganate aqueous solution with certain concentration, keeping the temperature for a certain time, washing a sample for three times by using ethanol, and drying the sample in an oven to obtain the manganese-doped cobaltosic oxide nanowire material, wherein the material improves the electron transmission rate and the capacitance performance, inhibits the cobaltosic oxide material from agglomerating, and has good flexibility and biocompatibility so as to enlarge the application range of the material; the electrostatic interaction between the capacitor material and the bacteria is enhanced, the electron transmission capability is improved, and the cell membrane of the bacteria is destroyed, so that the proliferation of the bacteria is inhibited.
2. The method for preparing a capacitive antibacterial material according to claim 1, wherein the method comprises the following steps: in the step S1), the cobalt salt is one or a combination of more of cobalt chloride, cobalt acetate, cobalt sulfate and cobalt nitrate;
The fluoride salt is one or a combination of more of ammonium fluoride, sodium fluoride, potassium fluoride or aluminum fluoride.
3. The method for preparing a capacitive antibacterial material according to claim 1, wherein the method comprises the following steps: in the step S1), the concentration of the cobalt salt is 0.15 mol/L;
the concentration of the fluoride salt is 0.28 mol/L;
the concentration of the urea is 0.7 mol/L.
4. The method for preparing a capacitive antibacterial material according to claim 1, wherein the method comprises the following steps: in the step S2), the pretreatment process of the carbon cloth is specifically to perform ultrasonic cleaning on the carbon cloth for 10min by respectively using 3mol/L dilute hydrochloric acid and ethanol, wherein the ultrasonic power is 320W.
5. The method for preparing a capacitive antibacterial material according to claim 4, wherein the method comprises the following steps: in the step S2), the temperature of the oven reaction is 80-180 ℃, and the reaction time is 2-10 h.
6. The method for preparing a capacitive antibacterial material according to claim 1, wherein the method comprises the following steps: step S2), S4), the drying temperature in the oven is 60 ℃, and the drying time is 12 h.
7. The method for preparing a capacitive antibacterial material according to claim 1, wherein the method comprises the following steps: in step S3), the annealing process specifically includes: after the temperature is increased to 100-500 ℃ at the temperature rising speed of 5 ℃/min, the temperature is kept for 0.5-5 h, and finally the temperature is reduced to the room temperature at the temperature reducing speed of 5 ℃/min.
8. The method for preparing a capacitive antibacterial material according to claim 1, wherein: in the step S4), the concentration of the potassium permanganate aqueous solution is 0.01-1 mol/L.
9. The method for preparing a capacitive antibacterial material according to claim 8, wherein: the reaction temperature is 100-200 ℃, and the reaction time is 0.5-3 h.
10. The method for preparing a capacitive antibacterial material according to claim 1, wherein: in the step S4), the concentration of the potassium permanganate aqueous solution is 0.03 mol/L;
the reaction temperature is 160 ℃, and the reaction time is 1 h.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017168352A1 (en) * | 2016-03-30 | 2017-10-05 | National Institute Of Food Technology Entrepreneurship And Management-Niftem | Antibacterial layered nanocomposite |
| CN107381660A (en) * | 2017-08-02 | 2017-11-24 | 上海纳米技术及应用国家工程研究中心有限公司 | Sb, Mn codope cobaltosic oxide nano flower-like microsphere preparation method |
| CN110237723A (en) * | 2019-06-21 | 2019-09-17 | 中国科学院烟台海岸带研究所 | A kind of magnesium doping antibacterial film and its preparation method and application |
| CN110252360A (en) * | 2019-06-28 | 2019-09-20 | 浙江理工大学 | A kind of cobalt manganese phosphorus sea urchin shape nano wire liberation of hydrogen catalysis material being grown on carbon cloth |
| CN112374545A (en) * | 2020-11-11 | 2021-02-19 | 湖北大学 | Transition metal ion doped manganous-manganic oxide nanosheet array based on carbon cloth growth and preparation method and application thereof |
| CN112931531A (en) * | 2021-02-08 | 2021-06-11 | 泉州师范学院 | Carbon-doped nickel phosphide composite antibacterial material and preparation method and application thereof |
| CN113040169A (en) * | 2021-03-09 | 2021-06-29 | 泉州师范学院 | Carbon doped MoS2/CoP/C composite antibacterial material and preparation method and application thereof |
| CN113295737A (en) * | 2021-05-17 | 2021-08-24 | 电子科技大学长三角研究院(湖州) | Manganese-doped cobaltosic oxide porous nano flaky material and preparation method and application thereof |
-
2022
- 2022-03-17 CN CN202210267804.2A patent/CN114668850B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017168352A1 (en) * | 2016-03-30 | 2017-10-05 | National Institute Of Food Technology Entrepreneurship And Management-Niftem | Antibacterial layered nanocomposite |
| CN107381660A (en) * | 2017-08-02 | 2017-11-24 | 上海纳米技术及应用国家工程研究中心有限公司 | Sb, Mn codope cobaltosic oxide nano flower-like microsphere preparation method |
| CN110237723A (en) * | 2019-06-21 | 2019-09-17 | 中国科学院烟台海岸带研究所 | A kind of magnesium doping antibacterial film and its preparation method and application |
| CN110252360A (en) * | 2019-06-28 | 2019-09-20 | 浙江理工大学 | A kind of cobalt manganese phosphorus sea urchin shape nano wire liberation of hydrogen catalysis material being grown on carbon cloth |
| CN112374545A (en) * | 2020-11-11 | 2021-02-19 | 湖北大学 | Transition metal ion doped manganous-manganic oxide nanosheet array based on carbon cloth growth and preparation method and application thereof |
| CN112931531A (en) * | 2021-02-08 | 2021-06-11 | 泉州师范学院 | Carbon-doped nickel phosphide composite antibacterial material and preparation method and application thereof |
| CN113040169A (en) * | 2021-03-09 | 2021-06-29 | 泉州师范学院 | Carbon doped MoS2/CoP/C composite antibacterial material and preparation method and application thereof |
| CN113295737A (en) * | 2021-05-17 | 2021-08-24 | 电子科技大学长三角研究院(湖州) | Manganese-doped cobaltosic oxide porous nano flaky material and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| HUIYU CHEN，ET: ""Uniform and porous Mn-doped Co3O4 microspheres: Solvothermal synthesis and their superior supercapacitor performances"", 《CERAMICS INTERNATIONAL》, vol. 45, 13 March 2019 (2019-03-13), pages 11876 - 11882 * |
| JIN LIU ET AL: ""Synthesis of MnO/C/Co3O4 nanocomposites by a Mn2+-oxidizing bacterium as a biotemplate for lithium-ion batteries"", 《SCIENCE AND TECHNOLOGY OF ADVANCED MATERIALS 》, vol. 22, no. 1, pages 429 - 440 * |
| JIN LIU，ET AL: ""Synthesis of MnO/C/Co3O4 nanocomposites by a Mn2+-oxidizing bacterium as a biotemplate for lithium-ion batteries"", 《SCIENCE AND TECHNOLOGY OF ADVANCED MATERIALS》, vol. 22, no. 1, 31 December 2021 (2021-12-31), pages 429 * |
| QI LIU, ET AL: ""N-doped carbon-coated Co3O4 nanosheet array/ carbon cloth for stable rechargeable Zn-air batteries"", 《SCIENCE CHINA MATERIALS》, vol. 62, no. 5, 5 November 2018 (2018-11-05), pages 624 * |
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