CN114668850B - Preparation method of capacitor antibacterial material - Google Patents
Preparation method of capacitor antibacterial material Download PDFInfo
- Publication number
- CN114668850B CN114668850B CN202210267804.2A CN202210267804A CN114668850B CN 114668850 B CN114668850 B CN 114668850B CN 202210267804 A CN202210267804 A CN 202210267804A CN 114668850 B CN114668850 B CN 114668850B
- Authority
- CN
- China
- Prior art keywords
- temperature
- sample
- oven
- antibacterial
- cobaltosic oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 143
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 83
- 239000003990 capacitor Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 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 120
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 59
- 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
- 239000004744 fabric Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000004202 carbamide Substances 0.000 claims abstract description 29
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 29
- 239000007864 aqueous solution Substances 0.000 claims abstract description 28
- 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 15
- 150000001868 cobalt Chemical class 0.000 claims abstract description 9
- 150000004673 fluoride salts Chemical class 0.000 claims abstract description 9
- 230000005540 biological transmission Effects 0.000 claims abstract description 8
- 230000009881 electrostatic interaction Effects 0.000 claims abstract description 5
- 238000005054 agglomeration Methods 0.000 claims abstract description 3
- 230000002776 aggregation Effects 0.000 claims abstract description 3
- 210000000170 cell membrane Anatomy 0.000 claims abstract description 3
- 230000035755 proliferation Effects 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 106
- 238000001035 drying Methods 0.000 claims description 55
- 239000002070 nanowire Substances 0.000 claims description 54
- 238000011010 flushing procedure Methods 0.000 claims description 50
- 238000001816 cooling Methods 0.000 claims description 27
- 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
- 238000010438 heat treatment Methods 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 11
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- 230000035484 reaction time 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
- 230000008569 process Effects 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
- 239000011572 manganese Substances 0.000 abstract description 18
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052748 manganese Inorganic materials 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 239000004809 Teflon Substances 0.000 description 46
- 229920006362 Teflon® Polymers 0.000 description 46
- 230000000052 comparative effect Effects 0.000 description 12
- 210000004027 cell Anatomy 0.000 description 10
- 230000001580 bacterial effect Effects 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 5
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 206010059866 Drug resistance Diseases 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 229940088710 antibiotic agent Drugs 0.000 description 3
- 230000004083 survival effect Effects 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 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 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 208000035143 Bacterial infection Diseases 0.000 description 1
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- 108010043121 Green Fluorescent Proteins Proteins 0.000 description 1
- 239000012980 RPMI-1640 medium Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 206010040829 Skin discolouration Diseases 0.000 description 1
- 206010052428 Wound Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal 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
- 238000004113 cell culture Methods 0.000 description 1
- 210000002390 cell membrane structure Anatomy 0.000 description 1
- 230000003833 cell viability Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001472 cytotoxic effect Effects 0.000 description 1
- 231100000263 cytotoxicity test Toxicity 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012091 fetal bovine serum Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 210000005260 human cell Anatomy 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100001083 no cytotoxicity Toxicity 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000037370 skin discoloration Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- 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)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dermatology (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Engineering & Computer Science (AREA)
- Communicable Diseases (AREA)
- Oncology (AREA)
- Carbon And Carbon Compounds (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a preparation method of a capacitor antibacterial material, which comprises the steps of sequentially dissolving cobalt salt, fluoride salt and urea with a certain concentration into deionized water to obtain a precursor solution; then, arranging the precursor solution and carbon in a Teflon-lined stainless steel autoclave, and reacting in an oven; and (3) annealing the sample, and then placing the sample in a potassium permanganate aqueous solution for reaction. According to the invention, the carbon cloth with a flexible three-dimensional network structure and high conductivity is used as a material carrier, so that not only can the electron transmission rate and the capacitance performance of the material be improved, but also the agglomeration of the cobaltosic oxide material is inhibited, and the application range of the material is enlarged due to the good flexibility and biocompatibility; the manganese doping can further improve the charge mass transmission and activity of the cobaltosic oxide, enhance the electrostatic interaction between the capacitance material and bacteria, improve the electron transmission capacity, destroy the cell membrane of the bacteria and inhibit the proliferation of the bacteria. The antibacterial activity is obviously improved. The colony count was only 10 0.5CFUmL‑1.
Description
Technical Field
The invention relates to the technical field of antibacterial materials, in particular to a preparation method of a capacitor antibacterial material.
Background
In the aspect of bacterial infection facing 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 drug resistance spectrum is also expanding continuously, so that the difficulty of clinical treatment and research of antibiotics is increasing. Fortunately, under the efforts of numerous researchers, a series of novel antibacterial materials capable of overcoming the traditional antibiotic short plates are continuously developed, such as silver-based antibacterial materials with the advantages of excellent antibacterial capability, long timeliness, difficult drug resistance generation and the like, and photocatalytic antibacterial materials (mainly comprising TiO2, znO) with the advantages of low cost, good antibacterial property, high biocompatibility and the like. Unfortunately, these antibacterial materials also have some non-negligible disadvantages, such as high cost, high toxicity, easy oxidation to cause skin discoloration, etc., and the antibacterial performance of the photocatalytic antibacterial materials is still to be improved. Based on the above circumstances, there is still an urgent need to develop an antibacterial material that satisfies the conditions of low cost, high biocompatibility, non-toxicity, high antibacterial activity, and the like at the same time.
In recent years, in a great deal of research, those skilled in the relevant art have found that bacteria with negative charges on the surface can destroy the cell membrane structure by electrostatic interaction with an antibacterial material with positive charges, thereby achieving sterilization and antibacterial effects. However, the surface charge of some antibacterial materials developed at present is still limited, and the antibacterial materials are rapidly neutralized after the electrostatic interaction with bacteria, so that the antibacterial materials are invalid and cannot meet the clinical long-acting antibacterial requirements. Therefore, it is of great significance to develop a low-cost, nontoxic, biocompatible, and biocompatible, capacitive antimicrobial material that can store a large amount of positive charges on the surface of the material by means of charging.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a capacitance antibacterial material with environmental protection, low cost, high antibacterial rate, long aging and good biocompatibility.
The technical scheme of the invention is as follows: the preparation method of the capacitor antibacterial material comprises the following steps:
s1), sequentially dissolving cobalt salt, fluoride salt and urea with a certain concentration into deionized water, and uniformly stirring at normal temperature to obtain a precursor solution;
S2), arranging the precursor solution and the pretreated carbon in a Teflon-lined stainless steel autoclave, reacting for a certain time in a baking oven with a certain temperature, flushing the obtained sample with ethanol for three times after the reaction is finished, and drying in the baking oven;
S3) placing the sample obtained in the step S2) in air with a certain temperature for annealing treatment 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 a certain concentration potassium permanganate aqueous solution, keeping the temperature for a certain time, flushing the sample for three times by using ethanol, and drying 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 several of cobalt chloride, cobalt acetate, cobalt sulfate or 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 to 0.5mol/L.
More preferably, in step S1), the concentration of the cobalt salt is 0.15mol/L.
Preferably, in step S1), the fluoride salt is one or a combination of several of ammonium fluoride, sodium fluoride, potassium fluoride and 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 to 0.5mol/L.
More preferably, in step S1), the fluoride salt concentration is 0.28mol/L.
Preferably, in the step S1), the urea concentration is 0.2 to 2mol/L.
More preferably, in step S1), the urea concentration is 0.7mol/L.
Preferably, in step S2), the pretreatment process of the carbon cloth specifically includes ultrasonic cleaning of the carbon cloth for 10min with 3mol/L diluted hydrochloric acid and ethanol, respectively, wherein the ultrasonic power is 320W.
Preferably, in 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 in the oven reaction is 120 ℃ and the reaction time is 6h.
Preferably, in steps S2) and S4), the drying temperature in the oven is 60 ℃ and the drying time is 12 hours.
Preferably, in step S3), the specific operation of the annealing treatment is as follows: after the temperature is raised to 100-500 ℃ at a temperature rising speed of 5 ℃/min, preserving heat for 0.5-5 h, and finally cooling the temperature to room temperature at a cooling speed of 5 ℃/min.
More preferably, in step S3), the annealing temperature is 350 ℃ and the annealing time is 2h.
Preferably, in the step S4), the concentration of the potassium permanganate aqueous solution is 0.01-1 mol/L.
More preferably, in the step S4), the concentration of the potassium permanganate aqueous solution is 0.03mol/L.
Preferably, in step S4), the reaction temperature is 100 to 200℃and the reaction time is 0.5 to 3 hours.
More preferably, in step S4), the reaction temperature is 160 ℃ and the reaction time is 1h.
The beneficial effects of the invention are as follows:
1. the manganese doped cobaltosic oxide capacitor antibacterial material obtained by simple and easy-to-operate hydrothermal reaction 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 electron transmission rate and the capacitance performance of the material can be improved, the agglomeration of the cobaltosic oxide material is inhibited, and the application range of the material is also enlarged due to the good flexibility and the biocompatibility;
2. The manganese doping can further improve the charge mass transmission and activity of the cobaltosic oxide, enhance the electrostatic interaction between the capacitance material and bacteria, improve the electron transmission capacity, destroy the cell membrane of the bacteria and inhibit 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, of the present invention;
FIG. 2 is an SEM image of a material according to an embodiment of the present invention, wherein (a) and (b) are respectively 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 C-Co/Mn material;
FIG. 3 is a graph showing the antibacterial effect of the material according to the present invention, wherein (a) (b) is the antibacterial effect of the C-Co prepared in comparative example 1 and the C-Co/Mn prepared in example 1 on E.coli, respectively, and (C) is the number of colonies after the C-Co and C-Co/Mn antibacterial materials act on E.coli.
FIG. 4 shows the death of cells after the action of the material according to the embodiment of the present invention, wherein (a) and (b) are the death of cells after the action of the C-Co prepared in comparative example 1 and the C-Co/Mn antibacterial material prepared in example 1, respectively.
Detailed Description
The following is a further description of embodiments of the invention, taken in conjunction with the accompanying drawings:
example 1
The embodiment provides a preparation method of a capacitor 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), arranging the precursor solution and the pretreated carbon in a 50mL Teflon lining stainless steel autoclave, reacting for 6 hours in a 120 ℃ oven, flushing the obtained sample with ethanol for three times after the reaction is finished, and drying in a 60 ℃ oven;
S3), placing the sample obtained in the S2) in air at 350 ℃ for annealing treatment for 2h. The specific operation of the annealing treatment is that the temperature is raised to 350 ℃ at the heating rate of 5 ℃/min, then the heat is preserved for 2 hours, finally the temperature is lowered to the room temperature at the cooling rate of 5 ℃/min, and then the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth is obtained;
S4), completely placing the C-Co sample obtained in the S3) into a 50mL Teflon lining stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, flushing the sample three times by ethanol, 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 capacitor 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), arranging the precursor solution and the pretreated carbon in a 50mL Teflon lining stainless steel autoclave, reacting for 6 hours in a 120 ℃ oven, flushing the obtained sample with ethanol for three times after the reaction is finished, and drying in a 60 ℃ oven;
S3), placing the sample obtained in the S2) in air at 350 ℃ for annealing treatment for 2h. The specific operation of the annealing treatment is that the temperature is raised to 350 ℃ at the heating rate of 5 ℃/min, then the heat is preserved for 2 hours, finally the temperature is lowered to the room temperature at the cooling rate of 5 ℃/min, and then the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth is obtained;
S4), completely placing the C-Co sample obtained in the S3) into a 50mL Teflon lining stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, flushing the sample three times by ethanol, 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 capacitor antibacterial material, which comprises the following steps:
S1), dissolving 0.15mol/L cobalt sulfate, 0.28mol/L ammonium fluoride and 0.7mol/L urea in 40mL deionized water in sequence, and stirring uniformly at normal temperature to obtain a precursor solution;
S2), arranging the precursor solution and the pretreated carbon in a 50mL Teflon lining stainless steel autoclave, reacting for 6 hours in a 120 ℃ oven, flushing the obtained sample with ethanol for three times after the reaction is finished, and drying in a 60 ℃ oven;
S3), placing the sample obtained in the S2) in air at 350 ℃ for annealing treatment for 2h. The specific operation of the annealing treatment is that the temperature is raised to 350 ℃ at the heating rate of 5 ℃/min, then the heat is preserved for 2 hours, finally the temperature is lowered to the room temperature at the cooling rate of 5 ℃/min, and then the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth is obtained;
S4), completely placing the C-Co sample obtained in the S3) into a 50mL Teflon lining stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, flushing the sample three times by ethanol, 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 capacitor 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), arranging the precursor solution and the pretreated carbon in a 50mL Teflon lining stainless steel autoclave, reacting for 6 hours in a 120 ℃ oven, flushing the obtained sample with ethanol for three times after the reaction is finished, and drying in a 60 ℃ oven;
S3), placing the sample obtained in the S2) in air at 350 ℃ for annealing treatment for 2h. The specific operation of the annealing treatment is that the temperature is raised to 350 ℃ at the heating rate of 5 ℃/min, then the heat is preserved for 2 hours, finally the temperature is lowered to the room temperature at the cooling rate of 5 ℃/min, and then the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth is obtained;
S4), completely placing the C-Co sample obtained in the S3) into a 50mL Teflon lining stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, flushing the sample three times by ethanol, 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 capacitor 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), arranging the precursor solution and the pretreated carbon in a 50mL Teflon lining stainless steel autoclave, reacting for 6 hours in a 120 ℃ oven, flushing the obtained sample with ethanol for three times after the reaction is finished, and drying in a 60 ℃ oven;
s3), placing the sample obtained in the S2) in air at 350 ℃ for annealing treatment for 2h. The specific operation of the annealing treatment is that the temperature is raised to 350 ℃ at the heating rate of 5 ℃/min, then the heat is preserved for 2 hours, finally the temperature is lowered to the room temperature at the cooling rate of 5 ℃/min, and then the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth is obtained;
S4), completely placing the C-Co sample obtained in the S3) into a 50mL Teflon lining stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, flushing the sample three times by ethanol, 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 capacitor 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), arranging the precursor solution and the pretreated carbon in a 50mL Teflon lining stainless steel autoclave, reacting for 6 hours in a 120 ℃ oven, flushing the obtained sample with ethanol for three times after the reaction is finished, and drying in a 60 ℃ oven;
S3), placing the sample obtained in the S2) in air at 350 ℃ for annealing treatment for 2h. The specific operation of the annealing treatment is that the temperature is raised to 350 ℃ at the heating rate of 5 ℃/min, then the heat is preserved for 2 hours, finally the temperature is lowered to the room temperature at the cooling rate of 5 ℃/min, and then the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth is obtained;
S4), completely placing the C-Co sample obtained in the S3) into a 50mL Teflon lining stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, flushing the sample three times by ethanol, 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 capacitor 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), arranging the precursor solution and the pretreated carbon in a 50mL Teflon lining stainless steel autoclave, reacting for 6 hours in a 120 ℃ oven, flushing the obtained sample with ethanol for three times after the reaction is finished, and drying in a 60 ℃ oven;
S3), placing the sample obtained in the S2) in air at 350 ℃ for annealing treatment for 2h. The specific operation of the annealing treatment is that the temperature is raised to 350 ℃ at the heating rate of 5 ℃/min, then the heat is preserved for 2 hours, finally the temperature is lowered to the room temperature at the cooling rate of 5 ℃/min, and then the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth is obtained;
S4), completely placing the C-Co sample obtained in the S3) into a 50mL Teflon lining stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, flushing the sample three times by ethanol, 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 capacitor 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), arranging the precursor solution and the pretreated carbon in a 50mL Teflon lining stainless steel autoclave, reacting for 6 hours in a 120 ℃ oven, flushing the obtained sample with ethanol for three times after the reaction is finished, and drying in a 60 ℃ oven;
S3), placing the sample obtained in the S2) in air at 350 ℃ for annealing treatment for 2h. The specific operation of the annealing treatment is that the temperature is raised to 350 ℃ at the heating rate of 5 ℃/min, then the heat is preserved for 2 hours, finally the temperature is lowered to the room temperature at the cooling rate of 5 ℃/min, and then the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth is obtained;
S4), completely placing the C-Co sample obtained in the S3) into a 50mL Teflon lining stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, flushing the sample three times by ethanol, 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 capacitor 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), arranging the precursor solution and the pretreated carbon in a 50mL Teflon lining stainless steel autoclave, reacting for 6 hours in a 120 ℃ oven, flushing the obtained sample with ethanol for three times after the reaction is finished, and drying in a 60 ℃ oven;
S3), placing the sample obtained in the S2) in air at 350 ℃ for annealing treatment for 2h. The specific operation of the annealing treatment is that the temperature is raised to 350 ℃ at the heating rate of 5 ℃/min, then the heat is preserved for 2 hours, finally the temperature is lowered to the room temperature at the cooling rate of 5 ℃/min, and then the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth is obtained;
S4), completely placing the C-Co sample obtained in the S3) into a 50mL Teflon lining stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, flushing the sample three times by ethanol, 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 capacitor 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), arranging the precursor solution and the pretreated carbon in a 50mL Teflon lining stainless steel autoclave, reacting for 6 hours in an oven at 80 ℃, flushing the obtained sample with ethanol for three times after the reaction is finished, and drying in the oven at 60 ℃;
S3), placing the sample obtained in the S2) in air at 350 ℃ for annealing treatment for 2h. The specific operation of the annealing treatment is that the temperature is raised to 350 ℃ at the heating rate of 5 ℃/min, then the heat is preserved for 2 hours, finally the temperature is lowered to the room temperature at the cooling rate of 5 ℃/min, and then the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth is obtained;
S4), completely placing the C-Co sample obtained in the S3) into a 50mL Teflon lining stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, flushing the sample three times by ethanol, 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 capacitor 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), arranging the precursor solution and the pretreated carbon in a 50mL Teflon lining stainless steel autoclave, reacting for 6 hours in a 180 ℃ oven, flushing the obtained sample with ethanol for three times after the reaction is finished, and drying in the 60 ℃ oven;
S3), placing the sample obtained in the S2) in air at 350 ℃ for annealing treatment for 2h. The specific operation of the annealing treatment is that the temperature is raised to 350 ℃ at the heating rate of 5 ℃/min, then the heat is preserved for 2 hours, finally the temperature is lowered to the room temperature at the cooling rate of 5 ℃/min, and then the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth is obtained;
S4), completely placing the C-Co sample obtained in the S3) into a 50mL Teflon lining stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, flushing the sample three times by ethanol, 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 capacitor 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), arranging the precursor solution and the pretreated carbon in a 50mL Teflon lining stainless steel autoclave, reacting for 3 hours in a 120 ℃ oven, flushing the obtained sample with ethanol for three times after the reaction is finished, and drying in a 60 ℃ oven;
S3), placing the sample obtained in the S2) in air at 350 ℃ for annealing treatment for 2h. The specific operation of the annealing treatment is that the temperature is raised to 350 ℃ at the heating rate of 5 ℃/min, then the heat is preserved for 2 hours, finally the temperature is lowered to the room temperature at the cooling rate of 5 ℃/min, and then the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth is obtained;
S4), completely placing the C-Co sample obtained in the S3) into a 50mL Teflon lining stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, flushing the sample three times by ethanol, 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 capacitor 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), arranging the precursor solution and the pretreated carbon in a 50mL Teflon lining stainless steel autoclave, reacting for 10 hours in a 120 ℃ oven, flushing the obtained sample with ethanol for three times after the reaction is finished, and drying in a 60 ℃ oven;
S3), placing the sample obtained in the S2) in air at 350 ℃ for annealing treatment for 2h. The specific operation of the annealing treatment is that the temperature is raised to 350 ℃ at the heating rate of 5 ℃/min, then the heat is preserved for 2 hours, finally the temperature is lowered to the room temperature at the cooling rate of 5 ℃/min, and then the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth is obtained;
S4), completely placing the C-Co sample obtained in the S3) into a 50mL Teflon lining stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, flushing the sample three times by ethanol, 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 capacitor 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), arranging the precursor solution and the pretreated carbon in a 50mL Teflon lining stainless steel autoclave, reacting for 6 hours in a 120 ℃ oven, flushing the obtained sample with ethanol for three times after the reaction is finished, and drying in a 60 ℃ oven;
S3), placing the sample obtained in the S2) in air at 350 ℃ for annealing treatment for 2h. The specific operation of the annealing treatment is that the temperature is raised to 150 ℃ at the heating rate of 5 ℃/min, then the heat is preserved for 2 hours, finally the temperature is lowered to the room temperature at the cooling rate of 5 ℃/min, and then the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth is obtained;
S4), completely placing the C-Co sample obtained in the S3) into a 50mL Teflon lining stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, flushing the sample three times by ethanol, 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 capacitor 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), arranging the precursor solution and the pretreated carbon in a 50mL Teflon lining stainless steel autoclave, reacting for 6 hours in a 120 ℃ oven, flushing the obtained sample with ethanol for three times after the reaction is finished, and drying in a 60 ℃ oven;
S3), placing the sample obtained in the S2) in air at 350 ℃ for annealing treatment for 2h. The specific operation of the annealing treatment is that the temperature is raised to 450 ℃ at the heating rate of 5 ℃/min, then the heat is preserved for 2 hours, and finally the temperature is lowered to the room temperature at the cooling rate of 5 ℃/min, and then the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth is obtained;
S4), completely placing the C-Co sample obtained in the S3) into a 50mL Teflon lining stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, flushing the sample three times by ethanol, 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 capacitor 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), arranging the precursor solution and the pretreated carbon in a 50mL Teflon lining stainless steel autoclave, reacting for 6 hours in a 120 ℃ oven, flushing the obtained sample with ethanol for three times after the reaction is finished, and drying in a 60 ℃ oven;
S3), placing the sample obtained in the S2) in air at 350 ℃ for annealing treatment for 2h. The specific operation of the annealing treatment is that the temperature is raised to 350 ℃ at the heating rate of 5 ℃/min, then the heat is preserved for 1h, finally the temperature is lowered to the room temperature at the cooling rate of 5 ℃/min, and then the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth is obtained;
S4), completely placing the C-Co sample obtained in the S3) into a 50mL Teflon lining stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, flushing the sample three times by ethanol, 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 capacitor 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), arranging the precursor solution and the pretreated carbon in a 50mL Teflon lining stainless steel autoclave, reacting for 6 hours in a 120 ℃ oven, flushing the obtained sample with ethanol for three times after the reaction is finished, and drying in a 60 ℃ oven;
S3), placing the sample obtained in the S2) in air at 350 ℃ for annealing treatment for 2h. The specific operation of the annealing treatment is that the temperature is raised to 350 ℃ at the heating rate of 5 ℃/min, then the temperature is kept for 4 hours, and finally the temperature is lowered to the room temperature at the cooling rate of 5 ℃/min, and then the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth is obtained;
S4), completely placing the C-Co sample obtained in the S3) into a 50mL Teflon lining stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, flushing the sample three times by ethanol, 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 capacitor 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), arranging the precursor solution and the pretreated carbon in a 50mL Teflon lining stainless steel autoclave, reacting for 6 hours in a 120 ℃ oven, flushing the obtained sample with ethanol for three times after the reaction is finished, and drying in a 60 ℃ oven;
s3), placing the sample obtained in the S2) in air at 350 ℃ for annealing treatment for 2h. The specific operation of the annealing treatment is that the temperature is raised to 350 ℃ at the heating rate of 5 ℃/min, then the heat is preserved for 2 hours, finally the temperature is lowered to the room temperature at the cooling rate of 5 ℃/min, and then the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth is obtained;
S4), completely placing the C-Co sample obtained in the S3) into a 50mL Teflon lining stainless steel autoclave containing 0.005mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, flushing the sample three times by ethanol, 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 capacitor 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), arranging the precursor solution and the pretreated carbon in a 50mL Teflon lining stainless steel autoclave, reacting for 6 hours in a 120 ℃ oven, flushing the obtained sample with ethanol for three times after the reaction is finished, and drying in a 60 ℃ oven;
S3), placing the sample obtained in the S2) in air at 350 ℃ for annealing treatment for 2h. The specific operation of the annealing treatment is that the temperature is raised to 350 ℃ at the heating rate of 5 ℃/min, then the heat is preserved for 2 hours, finally the temperature is lowered to the room temperature at the cooling rate of 5 ℃/min, and then the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth is obtained;
S4), completely placing the C-Co sample obtained in the S3) into a 50mL Teflon lining stainless steel autoclave containing 0.5mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 1h, flushing the sample three times by ethanol, 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 capacitor 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), arranging the precursor solution and the pretreated carbon in a 50mL Teflon lining stainless steel autoclave, reacting for 6 hours in a 120 ℃ oven, flushing the obtained sample with ethanol for three times after the reaction is finished, and drying in a 60 ℃ oven;
S3), placing the sample obtained in the S2) in air at 350 ℃ for annealing treatment for 2h. The specific operation of the annealing treatment is that the temperature is raised to 350 ℃ at the heating rate of 5 ℃/min, then the heat is preserved for 2 hours, finally the temperature is lowered to the room temperature at the cooling rate of 5 ℃/min, and then the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth is obtained;
S4), completely placing the C-Co sample obtained in the S3) into a 50mL Teflon lining stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 120 ℃ for 1h, flushing the sample three times by ethanol, 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 capacitor 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), arranging the precursor solution and the pretreated carbon in a 50mL Teflon lining stainless steel autoclave, reacting for 6 hours in a 120 ℃ oven, flushing the obtained sample with ethanol for three times after the reaction is finished, and drying in a 60 ℃ oven;
S3), placing the sample obtained in the S2) in air at 350 ℃ for annealing treatment for 2h. The specific operation of the annealing treatment is that the temperature is raised to 350 ℃ at the heating rate of 5 ℃/min, then the heat is preserved for 2 hours, finally the temperature is lowered to the room temperature at the cooling rate of 5 ℃/min, and then the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth is obtained;
S4), completely placing the C-Co sample obtained in the S3) into a 50mL Teflon lining stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 200 ℃ for 1h, flushing the sample three times by ethanol, 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 capacitor 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), arranging the precursor solution and the pretreated carbon in a 50mL Teflon lining stainless steel autoclave, reacting for 6 hours in a 120 ℃ oven, flushing the obtained sample with ethanol for three times after the reaction is finished, and drying in a 60 ℃ oven;
S3), placing the sample obtained in the S2) in air at 350 ℃ for annealing treatment for 2h. The specific operation of the annealing treatment is that the temperature is raised to 350 ℃ at the heating rate of 5 ℃/min, then the heat is preserved for 2 hours, finally the temperature is lowered to the room temperature at the cooling rate of 5 ℃/min, and then the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth is obtained;
S4), completely placing the C-Co sample obtained in the S3) into a 50mL Teflon lining stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 0.5h, flushing the sample three times by ethanol, 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 capacitor 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), arranging the precursor solution and the pretreated carbon in a 50mL Teflon lining stainless steel autoclave, reacting for 6 hours in a 120 ℃ oven, flushing the obtained sample with ethanol for three times after the reaction is finished, and drying in a 60 ℃ oven;
S3), placing the sample obtained in the S2) in air at 350 ℃ for annealing treatment for 2h. The specific operation of the annealing treatment is that the temperature is raised to 350 ℃ at the heating rate of 5 ℃/min, then the heat is preserved for 2 hours, finally the temperature is lowered to the room temperature at the cooling rate of 5 ℃/min, and then the cobaltosic oxide nanowire material (marked as C-Co) growing on the carbon cloth is obtained;
S4), completely placing the C-Co sample obtained in the S3) into a 50mL Teflon lining stainless steel autoclave containing 0.03mol/L potassium permanganate aqueous solution, keeping the temperature at 160 ℃ for 2 hours, flushing the sample three times by ethanol, and drying the sample in an oven at 60 ℃ for 12 hours to obtain the manganese-doped cobaltosic oxide nanowire material (marked as C-Co/Mn-23).
Comparative example 1
This comparative example provides a capacitor antibacterial material, which is different from example 1 in the preparation method thereof: s4, the step of the preparation process is not needed, and the preparation process is marked as C-Co.
Performance testing
1. Characterization of composition
Characterization results of the surface morphology of the antibacterial material prepared in example 1 and the antibacterial material of comparative example 1 are shown in fig. 1, and 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 the XRD patterns of both samples show signal peaks of tricobalt tetraoxide, which proves the successful preparation of tricobalt tetraoxide, but the XRD pattern of C-Co/Mn-1 does not show signal peaks of manganese, probably because the doping amount is low, and it is difficult to detect the signal peaks.
2. Morphology and elemental analysis
FIGS. 2 (a) and (b) are scanning electron microscope images (SEM) 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 tricobalt tetraoxide 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 manganese element does not have obvious influence on the morphology of cobaltosic oxide, and the nanowires are uniformly grown on the carbon cloth. To demonstrate successful doping of manganese, the study further performed 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, which demonstrates the successful preparation of the manganese doped tricobalt tetraoxide material.
3. Antibacterial experiments
Coli was inoculated into 10mL of LB medium and shaken at 37 ℃ for 18h at a rotational speed of 150 rpm. The bacterial suspension was diluted with PBS to a concentration of 10 8CFU mL-1. After all instruments and samples were scrubbed with 70% ethanol, the C-Co and C-Co/Mn electrodes with an active surface area of 1cm 2 were placed in the same PBS buffer, charged for 30min at 2V, the charged electrodes were wiped with clean paper towels to absorb the attached solution, then the electrodes were immersed in a semi-miniature plastic tube with 1mL of bacterial suspension (10 6CFU mL-1) PBS, treated for 15 and 30min, 10. Mu.L of the treated bacterial solution was taken and the coupon diluted. Antibacterial activity was determined by colony counting, 3 replicates per group. To verify the stability of the antibacterial properties, discharge antibacterial effect tests were performed on E.coli during a 7 cycle charge cycle using the same C-Co and C-Co/Mn electrodes. As shown in FIG. 3, the number of colonies after 60min of treatment of the C-Co/Mn antibacterial material is only 10 0.5CFU mL-1, and the number of colonies after 60min of treatment of the C-Co antibacterial material is still 10 5.5CFU mL-1, which shows that the 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 inoculated in 6-well plates (2X 10 5 cells per plate) with RPMI 1640 medium containing 10% fetal bovine serum, cultured for 24 hours, and the charged C-Co and C-Co/Mn electrodes were immersed in the cell culture solution, respectively, and further cultured for 24 hours. The treated cells were washed with PBS and then MTT reagent was added. After incubation for 4h at 37℃the crystals obtained were dissolved in DMSO and the absorbance was read on a 570nm wavelength microplate reader (Epoch 2, biotek) and simultaneously stained with a cell staining kit for qualitative analysis of cell viability. Live cells were stained with green fluorescent calcein AM and dead cells were stained with red fluorescent PI. Stained cells were imaged under a fluorescence microscope equipped with green and red filters. As shown in FIG. 4, the C-Co and C-Co/Mn capacitor antibacterial materials have no significant cytotoxic activity on cells, i.e., the C-Co and C-Co/Mn capacitor antibacterial materials have no cytotoxicity.
Table 1 antibacterial properties of antibacterial materials prepared in examples and comparative examples
As can be seen from table 1, the capacitor antibacterial material prepared by the preparation method of the present invention has excellent antibacterial activity, and in addition, the antibacterial material is nontoxic to human cells and environment-friendly (contains no heavy metal) compared with the capacitor antibacterial material in the example, the antibacterial material prepared in example 1 has excellent activity, and when the antibacterial material acts on bacteria, the bacterial survival rate (the bacterial colony number is only 10 0.5CFU mL-1) can be obviously reduced, and meanwhile, the bacterial survival rate (the bacterial colony number is only 10 5.5CFU mL-1) is also obviously lower than that under the action of the cobaltosic oxide antibacterial material of comparative example 1.
From the data of other examples, it can be seen that the preparation conditions (such as the kind and concentration of cobalt salt, the kind 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 antibacterial capacitor material. After the capacitance 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 merely to illustrate the principles and best modes of carrying out the invention, and various changes and modifications can be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (5)
1. The preparation method of the capacitor antibacterial material is characterized by comprising the following steps of:
s1), sequentially dissolving cobalt salt with the concentration of 0.15 mol/L, 0.28 mol/L fluoride salt and 0.7 mol/L urea into deionized water, and uniformly stirring at normal temperature to obtain a precursor solution;
S2), arranging the precursor solution and the pretreated carbon in a Teflon-lined stainless steel autoclave, reacting for a certain time in a baking oven with a certain temperature, flushing the obtained sample with ethanol for three times after the reaction is finished, and drying in the baking oven;
S3) placing the sample obtained in the step S2) in air with a certain temperature for annealing treatment for a certain time to obtain the cobaltosic oxide nanowire material growing on the carbon cloth;
S4), placing the cobaltosic oxide nanowire material obtained in the step S3) into a Teflon-lined stainless steel autoclave with a potassium permanganate aqueous solution with the concentration of 0.03 mol/L, after reacting at the temperature of 160 ℃ for 1 to h, flushing a sample for three times by ethanol, and drying in a drying oven to obtain the manganese-doped cobaltosic oxide nanowire material, wherein the material improves the electron transmission rate and the capacitance performance, inhibits the agglomeration of the cobaltosic oxide material, and increases the application range of the material due to good flexibility and biocompatibility; the electrostatic interaction between the capacitance material and bacteria is enhanced, the electron transmission capacity is improved, and the cell membrane of the bacteria is destroyed, so that the proliferation of the bacteria is inhibited;
In the step S1), the cobalt salt is one or a combination of a plurality of cobalt chloride, cobalt acetate, cobalt sulfate or cobalt nitrate;
The fluoride salt is one or a combination of more of ammonium fluoride, sodium fluoride, potassium fluoride and aluminum fluoride.
2. The method for preparing the antibacterial material for the capacitor according to claim 1, wherein the method comprises the following steps: in step S2), the pretreatment process of the carbon cloth specifically includes respectively performing ultrasonic cleaning on the carbon cloth with dilute hydrochloric acid and ethanol for 10min, where the ultrasonic power is 320W.
3. The method for preparing the antibacterial material for the capacitor according to claim 1, 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.
4. The method for preparing the antibacterial material for the capacitor according to claim 1, wherein the method comprises the following steps: in the steps S2) and S4), the drying temperature in the oven is 60 ℃ and the drying time is 12 h.
5. The method for preparing the antibacterial material for the capacitor according to claim 1, wherein the method comprises the following steps: in step S3), the specific operation of the annealing treatment is as follows: and (3) heating to 100-500 ℃ at a heating rate of 5 ℃/min, preserving heat for 0.5-5 h, and finally cooling to room temperature at a cooling rate of 5 ℃/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210267804.2A CN114668850B (en) | 2022-03-17 | 2022-03-17 | Preparation method of capacitor antibacterial material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210267804.2A CN114668850B (en) | 2022-03-17 | 2022-03-17 | Preparation method of capacitor antibacterial material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114668850A CN114668850A (en) | 2022-06-28 |
| CN114668850B true CN114668850B (en) | 2024-04-19 |
Family
ID=82074909
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210267804.2A Active CN114668850B (en) | 2022-03-17 | 2022-03-17 | Preparation method of capacitor antibacterial material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114668850B (en) |
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 |
|---|
| "N-doped carbon-coated Co3O4 nanosheet array/ carbon cloth for stable rechargeable Zn-air batteries";Qi Liu, et al;《SCIENCE CHINA Materials》;20181105;第62卷(第5期);624–632 * |
| "Synthesis of MnO/C/Co3O4 nanocomposites by a Mn2+-oxidizing bacterium as a biotemplate for lithium-ion batteries";Jin Liu et al;《SCIENCE AND TECHNOLOGY OF ADVANCED MATERIALS 》;第22卷(第1期);429-440 * |
| "Synthesis of MnO/C/Co3O4 nanocomposites by a Mn2+-oxidizing bacterium as a biotemplate for lithium-ion batteries";Jin Liu，et al;《SCIENCE AND TECHNOLOGY OF ADVANCED MATERIALS》;20211231;第22卷(第1期);429–440 * |
| "Uniform and porous Mn-doped Co3O4 microspheres: Solvothermal synthesis and their superior supercapacitor performances";Huiyu Chen，et;《Ceramics International》;20190313;第45卷;11876-11882 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114668850A (en) | 2022-06-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108300464B (en) | Preparation method of antibacterial N-doped carbon quantum dot, product and application thereof | |
| CN111909691A (en) | Preparation method of photo-thermal antibacterial near-infrared carbon quantum dots, product and application thereof | |
| CN111744552B (en) | Nano-enzyme bactericide based on bimetallic organic framework and preparation method and application thereof | |
| CN113244393B (en) | Titanium dioxide nanotube/molybdenum disulfide nanoflower compound and preparation method and application thereof | |
| CN108822838B (en) | Preparation method and application of copper-doped carbon quantum dots | |
| CN111495408B (en) | Visible light photocatalytic bactericide and preparation method and application thereof | |
| CN105132331A (en) | Komagataeibacter nataicola and application thereof | |
| CN114668850B (en) | Preparation method of capacitor antibacterial material | |
| CN114288406B (en) | Zn-MOF@Ti 3 C 2 T x Hybrid material, preparation method and application thereof | |
| CN106172386A (en) | A kind of preparation method carrying silver conch meal antibacterial | |
| CN109722242B (en) | Carbon quantum dot derived from lactobacillus and preparation method thereof | |
| CN112340822B (en) | Preparation method and application of nano zinc oxide/corn stalk composite antibacterial filter column | |
| CN110373891A (en) | Load bismuth tungstate/visible light-responded composite antibacterial fabric of titanium dioxide/redox graphene and preparation method thereof | |
| CN115722234A (en) | Ce-MoS with photodynamic-enzyme activity 2 /WO 3 Preparation method and application of nano composite antibacterial material | |
| CN112371104B (en) | Calcium titanate/bismuth titanate composite photocatalyst and preparation method and application thereof | |
| CN114318856B (en) | Antibacterial fiber, preparation method and application | |
| CN117431062B (en) | Preparation method and application of green luminous amino acid derivative antibacterial carbon dot | |
| CN114946857B (en) | Hollow polythiophene photocatalysis antibacterial agent and preparation method thereof | |
| CN115381963B (en) | Polydopamine/ferrous sulfide composite photo-thermal antibacterial material, and preparation method and application thereof | |
| CN114534758B (en) | Bismuth ferrite/graphite phase carbon nitride composite material and preparation method and application thereof | |
| CN116328824B (en) | Cerium oxide cluster nano-enzyme anchored by defective molecular sieve, and preparation method and application thereof | |
| CN113476644B (en) | Schiff base conjugated carbon nitride wound dressing and preparation method thereof | |
| CN114314658B (en) | Bismuth sulfide-transition metal carbide nano material, preparation method and application | |
| CN112321826B (en) | Preparation of flexible supermolecule perylene bisimide polymer and application of flexible supermolecule perylene bisimide polymer in visible light sterilization | |
| CN117463350A (en) | Cu (copper) alloy 2 O@ZnO visible light photocatalytic antibacterial material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |