CN113058622A - Nickel sulfide/molybdenum disulfide composite nano array for photoelectrocatalysis killing of drug-resistant bacteria and preparation method thereof - Google Patents
Nickel sulfide/molybdenum disulfide composite nano array for photoelectrocatalysis killing of drug-resistant bacteria and preparation method thereof Download PDFInfo
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- molybdenum disulfide
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- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 55
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 33
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 241000894006 Bacteria Species 0.000 title claims abstract description 18
- 239000003814 drug Substances 0.000 title claims abstract description 11
- 229940079593 drug Drugs 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
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- 230000000694 effects Effects 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 90
- 229910052759 nickel Inorganic materials 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 12
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- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 10
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- 239000011733 molybdenum Substances 0.000 claims description 10
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- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical group CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 7
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 7
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- 239000011593 sulfur Substances 0.000 claims description 6
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical group [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 claims description 5
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 3
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
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- 150000001875 compounds Chemical class 0.000 claims 1
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- 230000001580 bacterial effect Effects 0.000 description 6
- YGHCWPXPAHSSNA-UHFFFAOYSA-N nickel subsulfide Chemical compound [Ni].[Ni]=S.[Ni]=S YGHCWPXPAHSSNA-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
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- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 4
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- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- B01J35/33—
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- B01J35/39—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a nickel sulfide/molybdenum disulfide composite nano array for killing drug-resistant bacteria by photoelectrocatalysis and a preparation method thereof. The nickel sulfide/molybdenum disulfide composite nano array obtained by the invention has excellent sterilization effect and recovery performance, can quickly kill drug-resistant bacteria, can be directly washed and recovered by deionized water for reutilization after use, overcomes the defect that the traditional photocatalytic nano material cannot be recovered, and is more environment-friendly compared with the common photocatalytic nano material.
Description
Technical Field
The invention relates to the technical field of photoelectrocatalysis sterilization, in particular to a nickel sulfide/molybdenum disulfide composite nano array for photoelectrocatalysis sterilization of drug-resistant bacteria and a preparation method thereof.
Background
Drinking water safety is a significant problem worldwide, and the spread of many diseases has been caused by the presence of pathogenic microorganisms (including bacteria, modified microorganisms, fungi, bacteria, viruses, non-bacteria, etc.) in water bodies.
Conventional sterilization methods, including chlorine sterilization and heat sterilization (boiling), have many disadvantages, such as: possibly generating carcinogenic disinfection by-products, and residual chlorine affects the taste of drinking water and can not thoroughly kill encapsulated microorganisms. With the development of science and technology and the continuous updating of experimental means, the drinking water disinfection mode is gradually updated and advanced. The photoelectrocatalysis sterilization technology is favored because the photoelectrocatalysis sterilization technology can utilize external weak voltage to obviously improve the photocatalysis effect so as to efficiently solve the problem of environmental pollution. The technology has the advantages of stronger disinfection capability, environmental protection, secondary recovery, no generation of toxic and harmful byproducts, capability of realizing system self-purification, low energy consumption, mild reaction conditions, wide application range and capability of reducing secondary pollution. However, the existing photoelectrocatalysis antibacterial materials generally have the problems that the bacteria are difficult to effectively capture and the remineralization is continued. Therefore, the development of the photocatalytic antibacterial material capable of fixing bacteria and completely mineralizing the bacteria is of great significance.
Nano MoS2The photocatalyst has the characteristics of small size, large specific surface area, different surface chemical state and interior, incomplete surface atom coordination and the like, so that the photocatalyst has more surface active sites, uneven atom steps and enlarged reaction contact surface, is a good photocatalyst and also has certain sterilization capability. But due to thatThe material photogenerated electron hole pair is quickly compounded, and the nano molybdenum disulfide particles are difficult to recover after being dispersed in a water environment, so that secondary utilization cannot be realized, and the wide application of the molybdenum disulfide material in the field of sterilization is limited.
Disclosure of Invention
Based on the defects of the prior art, the invention provides a nickel sulfide/molybdenum disulfide composite nano array for killing drug-resistant bacteria by photoelectrocatalysis and a preparation method thereof, and the technical problems to be solved are that: ni driving under complex directional attachment process by using foamed nickel as substrate3S2Growth of nanoparticles to Ni3S2Nanorods and as a framework for guiding MoS2So as to obtain the nickel sulfide/molybdenum disulfide composite nano array which can be used as an anode electrode of a photoelectrocatalysis system.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a nickel sulfide/molybdenum disulfide composite nano array for photoelectrocatalysis killing of drug-resistant bacteria is characterized by comprising the following steps: uniformly mixing a surfactant, a sulfur source and a molybdenum source in deionized water, adding foamed nickel serving as a substrate, transferring the mixture into a hydrothermal reaction kettle, and carrying out hydrothermal reaction at the temperature of 200-220 ℃ for 20-24 hours; and after the reaction is finished, cooling to room temperature, taking out the sample, cleaning, drying in vacuum, then putting the sample into a tubular furnace, and calcining for 2-4 hours at 300-500 ℃ under the protection of nitrogen atmosphere to obtain the nickel sulfide/molybdenum disulfide composite nano array.
Preferably, the sulfur source is thioacetamide or thiourea, the molybdenum source is sodium molybdate dihydrate, and the surfactant is a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123). The addition of a proper amount of surfactant can assist the generation of the nano array.
Preferably, the dosage ratio of the surfactant to the molybdenum source to the deionized water is 0.05-2 g: 30-60 mg:30mL, and the mass ratio of the sulfur source to the molybdenum source is 1-2: 1.
Preferably, the temperature of the vacuum drying is 50-80 ℃, and the time is 6-12 h.
The nickel sulfide/molybdenum disulfide composite nano array obtained by the method is formed by taking foamed nickel as a substrate, forming a nickel sulfide nano rod array on the foamed nickel, and wrapping molybdenum sulfide nano particles on the surfaces of the nickel sulfide nano rods forming the array.
The nickel sulfide/molybdenum disulfide composite nano array can be used for a photoelectrocatalysis system, and drug-resistant bacteria can be killed through a photoelectrocatalysis effect under the conditions of visible light illumination and external voltage. Ni obtained in the present invention3S2@MoS2In the heterostructure, the MoS coated on the outer layer2The nanoparticles generate separation of photo-generated electron-hole pairs under the excitation of visible light irradiation. In the conventional MoS2In the nanoparticle material, electrons and holes can be rapidly compounded on the surface and in the interior of the molybdenum disulfide in a very short time, so that the sterilization performance of the molybdenum disulfide material is limited. In the material of the present invention, however, Ni3S2As a good metal conductor, Ni is given to electron edges3S2The capacity of the nano-rod to carry out rapid transportation to the nickel foam, under the dual actions of visible light illumination and external bias, photo-generated electron hole pairs are generated on the surface of the molybdenum disulfide, and photo-generated electrons are generated along Ni3S2The nano-rods are quickly separated and transferred to a counter electrode along an external circuit, and the structure of the composite material and the application method of photoelectric synergistic catalytic sterilization solve the problem that the traditional molybdenum disulfide material has the limitation effect on the sterilization performance due to the quick recombination of photo-generated electron hole pairs. And after the nickel sulfide/molybdenum disulfide composite nano array is used, the nickel sulfide/molybdenum disulfide composite nano array can be directly washed and recovered by deionized water for reutilization.
The invention has the beneficial effects that:
1. the nickel sulfide/molybdenum disulfide composite nano array obtained by the invention has excellent sterilization effect and recovery performance, can quickly kill drug-resistant bacteria, can be directly washed and recovered by deionized water for reutilization after use, overcomes the defect that the traditional photocatalytic nano material cannot be recovered, and is more environment-friendly compared with the common photocatalytic nano material.
2. The invention utilizes a nickel foam substrate and a surfactantThe MoS can be completed by a simple one-step hydrothermal synthesis method2And Ni3S2The ordered nano array deposition on the foam nickel has simple method and low manufacturing cost.
3. The raw material proportion and reaction temperature selected by the invention can lead Ni to be3S2@MoS2Is optimal, especially in regard to bactericidal properties.
Drawings
FIG. 1 shows Ni obtained in comparative example 2 of the present invention3S2SEM image of the nano-array;
FIG. 2 shows Ni obtained in example 1 of the present invention3S2@MoS2SEM image of the nano-array;
FIG. 3 shows Ni obtained in example 1 of the present invention3S2@MoS2HRTEM images of nanoarrays;
FIG. 4 shows Ni obtained in example 1 of the present invention3S2@MoS2XRD of nano-array versus standard card plot;
FIG. 5 shows Ni obtained in example 1 of the present invention3S2@MoS2EDS mapping of nanoarrays;
FIG. 6 shows the Nickel Foam (NF) of the blank control group obtained in comparative example 1 and the Ni obtained in comparative example 23S2Nanoarrays and Ni from example 13S2@MoS2Solid ultraviolet-visible diffuse reflectance spectroscopy of the nanoarray;
FIG. 7 shows Ni obtained in example 1 of the present invention3S2@MoS2Flat plate coating photo with sterilization effect of nano array under different times of visible light irradiation
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Comparative example 1
Cutting foamed nickel with the area of 1cm by 2cm, soaking for 20min by using 30mL of absolute ethyl alcohol, removing an oxidation layer possibly existing on the surface of the foamed nickel material, and then drying by using nitrogen for later use.
Adding the treated nickel foam into a 100mL beaker filled with 30mL deionized water, transferring the nickel foam into a high-pressure hydrothermal reaction kettle with a polytetrafluoroethylene substrate, and heating and preserving heat for 24 hours at 200 ℃; and cooling to room temperature after the reaction is finished, taking out the sample, washing the sample by using deionized water, carrying out vacuum drying at 60 ℃ for 6 hours, then putting the sample into a tubular furnace, heating to 400 ℃ at the heating rate of 10 ℃/min under the protection of nitrogen atmosphere, and carrying out heat preservation and calcination for 2 hours to obtain the blank control group foamed nickel material.
Comparative example 2
Cutting foamed nickel with the area of 1cm by 2cm, soaking for 20min by using 30mL of absolute ethyl alcohol, removing an oxidation layer possibly existing on the surface of the foamed nickel material, and then drying by using nitrogen for later use.
Uniformly mixing 0.1g P123 and 45mg thioacetamide in a 100mL beaker filled with 30mL deionized water, adding the processed foam nickel as a substrate, transferring the mixture into a high-pressure hydrothermal reaction kettle with a polytetrafluoroethylene substrate, and heating and preserving heat for 24 hours at 200 ℃; cooling to room temperature after the reaction is finished, taking out a sample, washing the sample by deionized water, drying the sample for 6 hours in vacuum at the temperature of 60 ℃, then putting the sample into a tubular furnace, heating the sample to 400 ℃ at the heating rate of 10 ℃/min under the protection of nitrogen atmosphere, and carrying out heat preservation and calcination for 2 hours to obtain the comparative Ni3S2And (4) nano arrays.
Example 1
Cutting foamed nickel with the area of 1cm by 2cm, soaking for 20min by using 30mL of absolute ethyl alcohol, removing an oxidation layer possibly existing on the surface of the foamed nickel material, and then drying by using nitrogen for later use.
Uniformly mixing 0.1g P123, 45mg thioacetamide and 45mg sodium molybdate dihydrate in a 100mL beaker filled with 30mL deionized water, adding the processed foam nickel as a base, transferring the mixture into a high-pressure hydrothermal reaction kettle with a polytetrafluoroethylene substrate, and heating and preserving heat for 24 hours at 200 ℃; cooling to room temperature after the reaction is finished, taking out a sample, washing the sample by deionized water, drying the sample at 60 ℃ in vacuum for 6 hours, then putting the sample into a tube furnace, heating the sample to 400 ℃ at the heating rate of 10 ℃/min under the protection of nitrogen atmosphere, and carrying out heat preservation and calcination for 2 hours to obtain Ni3S2@MoS2And (4) compounding the nano array.
Example 2
Cutting foamed nickel with the area of 1cm by 2cm, soaking for 20min by using 30mL of absolute ethyl alcohol, removing an oxidation layer possibly existing on the surface of the foamed nickel material, and then drying by using nitrogen for later use.
Uniformly mixing 0.1g P123, 60mg thioacetamide and 45mg sodium molybdate dihydrate in a 100mL beaker filled with 30mL deionized water, adding the processed foam nickel as a base, transferring the mixture into a high-pressure hydrothermal reaction kettle with a polytetrafluoroethylene substrate, and heating and preserving heat for 24 hours at 200 ℃; cooling to room temperature after the reaction is finished, taking out a sample, washing the sample by deionized water, drying the sample at 60 ℃ in vacuum for 6 hours, then putting the sample into a tube furnace, heating the sample to 400 ℃ at the heating rate of 10 ℃/min under the protection of nitrogen atmosphere, and carrying out heat preservation and calcination for 2 hours to obtain Ni3S2@MoS2And (4) compounding the nano array.
Example 3
Cutting foamed nickel with the area of 1cm by 2cm, soaking for 20min by using 30mL of absolute ethyl alcohol, removing an oxidation layer possibly existing on the surface of the foamed nickel material, and then drying by using nitrogen for later use.
Uniformly mixing 0.1g P123, 90mg thioacetamide and 45mg sodium molybdate dihydrate in a 100mL beaker filled with 30mL deionized water, adding the processed foam nickel as a base, transferring the mixture into a high-pressure hydrothermal reaction kettle with a polytetrafluoroethylene substrate, and heating and preserving heat for 24 hours at 200 ℃; cooling to room temperature after the reaction is finished, taking out a sample, washing the sample by deionized water, drying the sample at 60 ℃ in vacuum for 6 hours, then putting the sample into a tube furnace, heating the sample to 400 ℃ at the heating rate of 10 ℃/min under the protection of nitrogen atmosphere, and carrying out heat preservation and calcination for 2 hours to obtain Ni3S2@MoS2And (4) compounding the nano array.
FIG. 1 shows Ni obtained in comparative example 23S2SEM image of the nanoarray from which Ni can be seen3S2And (4) generating a nano array.
FIG. 2 shows Ni obtained in example 13S2@MoS2SEM image of composite nanoarray, from which it can be seen that Ni constituting the array3S2The surface of the nano rod is coated with MoS2And (3) nanoparticles.
FIG. 3 shows Ni obtained in example 13S2@MoS2HRTEM image of nano-array, FIG. 4 is Ni obtained in example 13S2@MoS2The XRD spectrum of the nano array is compared with that of a standard card. The characteristic peaks at 2 theta ≈ 14 DEG and 32 DEG in the XRD spectrum of the material correspond to MoS2(002) crystal face and Ni3S2Crystal face (021) of (g), and MoS is obtained by calculation2(002) Lattice spacing d of crystal planes002＝0.615nm，Ni3S2(021) Lattice spacing d of crystal planes0210.234nm, which is consistent with data obtained from high-resolution projection electron microscopy (HRTEM), confirming Ni3S2@MoS2Successfully synthesized on the surface of the foamed nickel.
FIG. 5 shows Ni obtained in example 13S2@MoS2The EDS mapping of the nano array shows that the distribution of three elements of Mo, S and Ni exists on the surface of the nano array.
FIG. 6 shows the blank Nickel Foam (NF) obtained in comparative example 1 and Ni obtained in comparative example 23S2Nanoarrays and Ni from example 13S2@MoS2Solid UV-Vis Diffuse reflectance Spectrum for nanoarrays, as seen at MoS2After coating, Ni from example 13S2@MoS2The visible light absorption range of the nano array material is widened, and the visible light can be better absorbed and utilized.
The samples obtained in the above examples were tested for bactericidal effect as follows:
a. preparation before experiment: preparing a plurality of 15mL glass test tubes, a plurality of 5mL glass test tubes, a plurality of 1.5mL centrifuge tubes, a lactose bile salt fermentation medium (LB), a lactose bile salt agar fermentation solid medium and a PBS buffer solution, performing high-pressure steam sterilization (121 ℃, 40min) for later use, cooling the lactose bile salt agar fermentation solid medium to 60 ℃, pouring a flat plate, and waiting for solidification to form a solid culture dish.
b. Shaking the bacteria: adding 10-12mL lactose bile salt fermentation medium (LB) into 15mL glass test tube, inoculating Escherichia coli, placing in constant temperature oscillator, culturing at 37 deg.C and 160r/min for 18-20 hr to make colony count reach about 5 × 108CFU/mL。
c. And (4) sucking 3 mu L of the bacterial liquid obtained in the step b by using a pipette gun, adding the bacterial liquid into 4mL of deionized water, and uniformly shaking.
d. Taking 70 mu L of the bacterial suspension obtained in the step c into 70mL of PBS buffer solution, and uniformly mixing to obtain a mixed solution; the samples prepared in the respective examples were loaded on sample anode clamps, and a platinum electrode was used as an electrode cathode, and a PBS buffer solution was used as an electrolyte, to which a bias of 0.42V was applied.
e. And (3) irradiating the photoelectrocatalysis reaction system in the step d by using a 1.5W LED lamp in a photocatalysis reaction box, sucking 50 mu L of bacterial liquid from the solution by using a pipette gun at intervals of 5 minutes, coating a flat plate, placing the culture dish in a constant-temperature incubator for culture (the culture temperature is 30-37 ℃, and the culture time is 24-36 hours), and counting.
f. After the experiment was completed, the used sample of example 1 was recovered, the surface of the sample was washed with deionized water, the above experimental steps were repeated after the sample was naturally air-dried, and the number of colonies was recorded.
The results of the bactericidal performance test of the samples obtained in each example are shown in table 1.
TABLE 1
| Sample (I) | 0min | 5min | 10min | 15min | 20min | 25min | Rate of sterilization |
| Example 1 (photoelectrocatalysis) | 277 | 300 | 110 | 50 | 3 | 0 | 100％ |
| Example 2 (photoelectrocatalysis) | 310 | 320 | 280 | 140 | 90 | 19 | 93％ |
| Example 3 (photoelectrocatalysis) | 291 | 329 | 232 | 149 | 95 | 69 | 76％ |
| Comparative example 2 (photoelectrocatalysis) | 289 | 310 | 296 | 287 | 275 | 269 | 6％ |
| Example 1 (secondary test after recovery) | 314 | 328 | 206 | 93 | 20 | 2 | 99％ |
| Example 1 (not energized in dark conditions) | 300 | 320 | 300 | 296 | 298 | 292 | 2％ |
By comparison, Ni obtained in each example3S2@MoS2The performance of the composite nano array is obviously superior to that of Ni obtained in comparative example 23S2And (4) nano arrays. The material obtained without adding a molybdenum source has poor photoelectrocatalysis sterilization performance, mainly because the molybdenum source is lacked, molybdenum disulfide cannot be generated, the molybdenum disulfide can absorb visible light to generate active oxygen, and the active oxygen attacks bacterial cell membranes in large quantity to cause damage to bacterial membrane structures. When the mass ratio of the added sodium molybdate to the thioacetamide is 1:1, the sterilization performance is best. At the same time, it is known that Ni3S2@MoS2Has excellent recycling performance.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Any person skilled in the art may, using the teachings disclosed above, change or modify the equivalent embodiments with equivalent changes. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (7)
1. A preparation method of a nickel sulfide/molybdenum disulfide composite nano array for photoelectrocatalysis killing of drug-resistant bacteria is characterized by comprising the following steps: uniformly mixing a surfactant, a sulfur source and a molybdenum source in deionized water, adding foamed nickel serving as a substrate, transferring the mixture into a hydrothermal reaction kettle, and carrying out hydrothermal reaction at the temperature of 200-220 ℃ for 20-24 hours; and after the reaction is finished, cooling to room temperature, taking out the sample, cleaning, drying in vacuum, then putting the sample into a tubular furnace, and calcining for 2-4 hours at 300-500 ℃ under the protection of nitrogen atmosphere to obtain the nickel sulfide/molybdenum disulfide composite nano array.
2. The method of claim 1, wherein: the sulfur source is thioacetamide or thiourea, the molybdenum source is sodium molybdate dihydrate, and the surfactant is a triblock copolymer of polyethylene oxide-polypropylene oxide-polyethylene oxide.
3. The method of claim 1, wherein: the dosage ratio of the surfactant to the molybdenum source to the deionized water is 0.05-2 g: 30-60 mg:30 mL; the mass ratio of the sulfur source to the molybdenum source is 1-2: 1.
4. The method of claim 1, wherein: the temperature of vacuum drying is 50-80 ℃, and the time is 6-12 h.
5. A nickel sulfide/molybdenum disulfide composite nano array obtained by the preparation method of any one of claims 1 to 4.
6. The nickel sulfide/molybdenum disulfide composite nanoarray of claim 5, wherein: the nickel sulfide/molybdenum disulfide composite nano array is formed by taking foamed nickel as a substrate, forming a nickel sulfide nano rod array on the foamed nickel, and wrapping molybdenum sulfide nano particles on the surfaces of nickel sulfide nano rods forming the array.
7. Use of a nickel sulphide/molybdenum disulphide composite nanoarray according to claim 5 or 6, characterized in that: the compound is used for a photoelectrocatalysis system, and under the conditions of visible light illumination and external voltage, drug-resistant bacteria are killed through a photoelectrocatalysis effect; and after the nickel sulfide/molybdenum disulfide composite nano array is used, the nickel sulfide/molybdenum disulfide composite nano array can be directly washed and recovered by deionized water for reutilization.
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