CN113925059A - Molybdenum disulfide/fullerene semiconductor composite photocatalytic bactericide and preparation method thereof - Google Patents
Molybdenum disulfide/fullerene semiconductor composite photocatalytic bactericide and preparation method thereof Download PDFInfo
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- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 61
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 41
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- 239000003899 bactericide agent Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
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- 229910052799 carbon Inorganic materials 0.000 claims abstract description 47
- 239000000758 substrate Substances 0.000 claims abstract description 8
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 28
- 238000002485 combustion reaction Methods 0.000 claims description 16
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- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- -1 m-trimethylbenzene Chemical compound 0.000 claims description 3
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 2
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- 150000001875 compounds Chemical class 0.000 claims 1
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 32
- 229910052786 argon Inorganic materials 0.000 description 16
- 229910052961 molybdenite Inorganic materials 0.000 description 13
- 241000588724 Escherichia coli Species 0.000 description 12
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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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
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Images
Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/16—Disinfection, sterilisation or deodorisation of air using physical phenomena
- A61L9/18—Radiation
-
- 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
-
- B01J35/39—
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2101/00—Chemical composition of materials used in disinfecting, sterilising or deodorising
- A61L2101/02—Inorganic materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2101/00—Chemical composition of materials used in disinfecting, sterilising or deodorising
- A61L2101/02—Inorganic materials
- A61L2101/14—Inorganic materials containing sulfur
Abstract
The invention discloses a molybdenum disulfide/fullerene semiconductor composite photocatalytic bactericide and a preparation method thereof. The carbon paper is used as the substrate for the growth of the molybdenum disulfide, the aggregation of the molybdenum disulfide in aqueous solution is avoided, the material is more convenient to recover, and the separation of electron-hole pairs in the molybdenum disulfide is facilitated through the recombination of fullerene, so that the composite material has excellent photocatalytic sterilization performance.
Description
Technical Field
The invention relates to a molybdenum disulfide/fullerene semiconductor composite photocatalytic bactericide and a preparation method thereof, belonging to the field of photocatalysis.
Background
With the rapid development of industry, environmental issues have received a great deal of attention throughout society. Among the numerous contaminants, bacteria are widely present in nature in water and soil, hospital-discharged sewage, including common escherichia coli, staphylococcus aureus, etc., which pose a threat to human health and social development. In recent years, the photocatalytic technology has attracted attention because it can solve the problem of environmental pollution using solar energy, and among them, a photocatalyst having good antibacterial properties is prominent. By preparing the high-efficiency photocatalyst and reasonably applying the photocatalyst to the antibacterial field, part of the problem of bacterial pollution can be effectively solved.
MoS2The graphene oxide semiconductor material is an excellent semiconductor material, is one of representatives of transition metal sulfides, has a graphene-like layered structure, and has good optical and electrical properties. Generally, bulk or nano-layered molybdenum disulfide is an indirect bandgap semiconductor, the energy gap of the bulk molybdenum disulfide is about 1.20eV, the energy gap of two-dimensional layered molybdenum disulfide increases with the decrease of the number of layers, and the energy gap of a single layer of molybdenum disulfide can reach 1.89 eV. The molybdenum disulfide has high specific surface area, good biocompatibility and stability, can improve the performance of the molybdenum disulfide by doping or modification, has abundant active catalytic sites at exposed edge positions, and can be considered as an antibacterial material. The single molybdenum disulfide has limited antibacterial activity, aggregation occurs in an aqueous solution to reduce the antibacterial activity of the molybdenum disulfide, and how to improve the antibacterial activity of the molybdenum disulfide is widely applied, thereby attracting wide attention of researchers. The fullerene has a unique pi-electron conjugated system, can be used as an electron acceptor to capture electrons, and is used for modifying a semiconductorThe method is used in the field of photocatalysis, after the photo-excited semiconductor generates electron-hole pairs, photo-generated electrons are easily captured by fullerene to be transferred, the recombination probability of the electron-hole pairs in the semiconductor is reduced, and the catalytic activity of the semiconductor is obviously improved. Therefore, if the MoS is modified with an appropriate amount of fullerene by an appropriate method2The aggregation phenomenon can be reduced, and the catalytic activity of the material is improved, so that the material has higher antibacterial activity.
Disclosure of Invention
The invention provides a molybdenum disulfide/fullerene semiconductor composite photocatalytic bactericide and a preparation method thereof, aiming at effectively improving the photocatalytic bactericidal performance of molybdenum disulfide.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention discloses a preparation method of a molybdenum disulfide/fullerene semiconductor composite photocatalytic bactericide, which is characterized by comprising the following steps: the composite photocatalytic bactericide is obtained by synthesizing molybdenum disulfide on a carbon paper substrate and modifying the molybdenum disulfide by fullerene. The carbon paper is used as a substrate for growth of the molybdenum disulfide, can be applied to photocatalytic reaction, avoids aggregation of the molybdenum disulfide in aqueous solution, and simultaneously enables the material to be recovered more conveniently. The fullerene is helpful for promoting the separation of electron-hole pairs in the molybdenum disulfide, thereby improving the photocatalytic sterilization performance of the molybdenum disulfide.
The preparation method specifically comprises the following steps:
(1) placing a combustion boat filled with molybdenum trioxide in the center of a tube furnace, placing carbon paper at the downstream, heating to 850 ℃ under the protection of argon atmosphere, keeping the temperature for 10min, and naturally cooling to room temperature to deposit molybdenum trioxide on the carbon paper;
(2) placing the combustion boat filled with sulfur powder in the center of a tube furnace, placing the carbon paper in the step 1 at the downstream, heating to 400 ℃ under the protection of argon atmosphere, preserving the heat for 20min, and naturally cooling to room temperature to convert molybdenum trioxide on the carbon paper into molybdenum dioxide;
(3) placing a combustion boat filled with sulfur powder with the same amount as the sulfur powder in the step 2 in the center of a tube furnace, placing the carbon paper in the step 2 at the downstream, heating to 850 ℃ under the protection of argon atmosphere, preserving the heat for 20min, and naturally cooling to room temperature to convert molybdenum dioxide on the carbon paper into molybdenum disulfide;
(4) and (3) dissolving fullerene powder in an organic solvent, then immersing the carbon paper obtained in the step (3) in the solution, taking out and drying to obtain the target product molybdenum disulfide/fullerene composite photocatalytic bactericide.
Further, the fullerene is C60Or C70。
Further, the mass ratio of the molybdenum trioxide in the step (1) to the sulfur powder in the step (2) is 1: 5-30.
Further, the temperature increase rate in the steps (1) to (3) was 20 ℃/min.
Further, in the step (4), the concentration of the fullerene powder in the organic solvent is 0.5-0.6 mg/mL.
Further, in the step (4), the carbon paper is immersed in the solution for 1 min.
Further, in the step (4), the drying is carried out in a vacuum oven at 120 ℃ for 4h, and then the temperature is reduced to 80 ℃ for 10-12 h.
Further, in the step (4), the organic solvent is any one of carbon disulfide, carbon tetrachloride, p-xylene, o-xylene, m-trimethylbenzene, toluene, chlorobenzene, and dichlorobenzene.
The molybdenum disulfide/fullerene semiconductor composite nanomaterial synthesized according to the steps is characterized in that carbon paper is used as a substrate, a molybdenum disulfide sheet layered structure is formed on the carbon paper, and fullerene crystals are bonded on the surface of the layered molybdenum disulfide.
The molybdenum disulfide/fullerene semiconductor composite nano material is synthesized on a carbon paper substrate and can be clamped on an electrode clamp to be used in a photocatalytic system. Under the irradiation of visible light, active free radicals are generated through a photocatalytic effect to kill bacteria such as escherichia coli. The single molybdenum disulfide nano material can generate separation of photo-generated electron-hole pairs under the irradiation of visible light, but before the reaction of holes with oxidability and electrons with reducibility, the holes and the electrons with reducibility can be quickly compounded on the surface and the inside of molybdenum disulfide in a very short time, and the high electron-hole recombination rate can seriously hinder the catalytic performance of the molybdenum disulfide, thereby influencing the antibacterial performance of the material. According to the invention, the molybdenum disulfide and the fullerene are compounded to form the heterostructure, the energy gap of the molybdenum disulfide is reduced by the compounded fullerene, and the utilization rate of the heterostructure on visible light is improved. Under the irradiation of visible light, electrons and holes generated by light excitation are separated, and after the electrons jump from a valence band to a conduction band, part of the electrons are transferred to the conduction band of fullerene with strong electron accepting capability, so that the probability of recombination of the electrons returning to the original valence band and the holes is reduced, the catalytic efficiency of the semiconductor catalyst is greatly improved, and the antibacterial efficiency of the semiconductor material is improved.
The invention has the beneficial effects that:
1. the molybdenum disulfide/fullerene composite material deposited on the carbon paper substrate has excellent antibacterial performance compared with a single material, has the advantage of easy recovery compared with the traditional nano granular material, and better meets the requirements of environmental protection.
2. Fullerene is a typical electronegative molecule and can be used as an electron acceptor in the field of catalysis. According to the invention, the lamellar molybdenum disulfide synthesized by using fullerene is modified, so that the electron mobility and the separation efficiency of electron-hole pairs in a molybdenum disulfide semiconductor can be effectively improved, and the antibacterial performance of the obtained composite material is obviously improved.
3. The composite material of the invention has simple synthesis method and simple and convenient operation.
4. According to the invention, the raw material ratio, the reaction temperature and the reaction time are regulated and controlled, so that the prepared composite nano material has an excellent effect of killing escherichia coli.
Drawings
FIG. 1 shows lamellar nano-MoS obtained in example 1 of the present invention2A Scanning Electron Microscope (SEM) image of (a);
FIG. 2 shows MoS obtained in example 1 of the present invention2/C60A Scanning Electron Microscope (SEM) image of the composite material;
FIG. 3 shows the lamellar nano-MoS obtained in example 1 of the present invention2R of (A) to (B)an aman map;
FIG. 4 shows MoS obtained in example 1 of the present invention2/C60Composite material and lamellar nano MoS2A relational graph of the change of the survival rate of the escherichia coli with the antibacterial time when the escherichia coli is treated under the dark condition;
FIG. 5 shows MoS obtained in example 1 of the present invention2/C60Composite material and lamellar nano MoS2Graph showing the relationship between the survival rate of Escherichia coli and the antibacterial time when Escherichia coli was treated under simulated irradiation with visible light.
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.
Example 1
This example prepares MoS as follows2/C60The composite material comprises the following components:
(1) cutting carbon paper with area of 1 × 7cm, placing an alumina combustion boat containing 90.8mg of molybdenum trioxide powder in the center of a tube furnace, introducing argon gas into the upstream, and placing the carbon paper at the position of about 4cm away from the combustion boat in the downstream. At the beginning, argon is introduced for 30min to exhaust the air in the tube furnace, then the tube furnace is heated to 850 ℃ at the heating rate of 20 ℃/min under the protection of argon, the temperature is kept for 10min at the temperature, and finally the tube furnace is naturally cooled to the room temperature. This step allowed molybdenum trioxide to be deposited on the carbon paper.
(2) The combustion boat and the carbon paper are taken out of the tube furnace, the alumina combustion boat containing 600.1mg of sulfur powder is arranged in the center of the tube furnace, argon is introduced into the upstream, and the carbon paper is arranged at the position which is about 4cm away from the combustion boat in the downstream. At the beginning, argon is introduced for 30min to exhaust the air in the tube furnace, then the tube furnace is heated to 400 ℃ at the heating rate of 20 ℃/min under the protection of argon, the temperature is kept for 20min at the temperature, and finally the tube furnace is naturally cooled to the room temperature. This step converts the molybdenum trioxide on the carbon paper to molybdenum dioxide.
(3) Re-weighing 600.1mg of sulfur powder to replace the sulfur powder in the step (2), and introducing argon gas for 30min is discharged to the inside of the tube furnace. Heating the tube furnace to 850 ℃ at the heating rate of 20 ℃/min under the protection of argon, preserving the heat for 20min at the temperature, and finally naturally cooling the tube furnace to room temperature to obtain the lamellar nano MoS deposited on the carbon paper2。
(4) 20mL of carbon tetrachloride solution was measured and poured into a beaker, and 10.1mg of fullerene (C) was weighed60) It was completely dissolved in carbon tetrachloride solution. Will deposit lamellar nano MoS2The carbon paper is put into the solution to be soaked for 1min, taken out and put into a vacuum oven, firstly baked for 4h at 120 ℃, then cooled to 80 ℃ and baked for 12h, finally the vacuum oven is naturally cooled to room temperature, and a sample is taken out to obtain a target product: MoS deposited on carbon paper2/C60A composite material.
FIG. 1 shows the lamellar nano-MoS obtained in step (3) of this example2From the SEM image, MoS was clearly observed2In a sheet-like structure.
FIG. 2 shows the MoS obtained in step (4) of this example2/C60SEM image of composite material, from which lamellar nano MoS can be observed2The surface is attached with fullerene particles.
FIG. 3 shows the lamellar nano-MoS obtained in step (3) of this example2Can be seen from the graph of 383.1cm-1、408.4cm-1Corresponds to molybdenum disulfide E2g、A1gPeak of vibration mode.
The antibacterial effect of the material obtained in this example was tested as follows:
(1) inoculating the Escherichia coli stock solution into sterilized liquid lactose bile salt fermentation medium, and culturing overnight in constant temperature shaking table at 37 deg.C and 220rpm to obtain Escherichia coli suspension. Preparing a solid lactose bile salt fermentation medium, sterilizing at high temperature (121 ℃, 20min), and putting into an oven (60 ℃) for later use. A number of 5mL centrifuge tubes, PBS buffer, sterile water, disposable petri dishes were prepared for use.
(2) And pouring the solid lactose bile salt fermentation medium into a disposable culture dish, namely a plate pouring process, and placing aside until the solid lactose bile salt fermentation medium is solidified. 4mL of sterile water and 20. mu.L of the E.coli suspension cultured overnight in step (1) were pipetted into a 5mL centrifuge tube using a pipette gun, and mixed by shaking.
(3) And (3) adding 70ml of LPBS buffer solution into a beaker to serve as electrolyte, using a liquid transfer gun to transfer 70 mu L of diluted bacterial liquid from the centrifugal tube in the step (2), putting a rotor into the beaker, and uniformly mixing the buffer solution and the bacterial liquid by using magnetic stirring. Cutting 1 x 1cm area of the lamellar nano MoS obtained in the step (3)2Sample or MoS obtained in step (4)2/C60And clamping the composite material sample on the electrode clamp for standby.
(4) In the reaction box, an 18W LED lamp is used as a light source to irradiate the photocatalytic reaction system in the step (3), 30 mu L of bacterial liquid is removed from a beaker by using a liquid removing gun at intervals of 30 minutes to carry out plate coating, the culture dish is inverted to carry out culture in a biochemical constant temperature culture box (the culture temperature is 35-37 ℃, the culture time is 24-36 hours), and the survival rate of the bacteria is determined by counting colonies on the culture medium. In the experiment, each sampling is carried out twice as a parallel control, and the average value is taken as the final result.
(5) In order to test the effect of light on the performance of the composite material, the test results of dark treatment (same steps as the photocatalytic treatment method, except that no light is applied and the antibacterial reaction is performed in the dark) are used as comparison.
FIG. 4 shows the MoS obtained in this example2/C60Composite material and lamellar nano MoS2And (3) performing an antibacterial experiment for 3h under a dark condition, and obtaining a relation graph of the change of the survival rate of the escherichia coli along with the antibacterial time. As can be seen in the figure, under dark conditions, a single MoS2And MoS2/C60The composite material has only weak antibacterial performance.
FIG. 5 shows the MoS obtained in this example2/C60Composite material and lamellar nano MoS2And only deposit C60The carbon paper and the blank carbon paper (CFP, the detection method of the antibacterial performance is the same as the steps) are subjected to an antibacterial experiment for 3h under the condition of simulated illumination, and a relation graph of the survival rate of escherichia coli along with the change of antibacterial time is shown. Compared with the antibacterial experiment under dark conditions, C60And a blank carbon paper having substantially no antibacterial activity, and MoS2/C60、MoS2The antibacterial rate of (A) is greatly improved, wherein MoS2/C60The survival rate of bacteria after the composite material is subjected to an antibacterial experiment for 3 hours is less than 1 percent, and the antibacterial efficiency is far higher than that of single MoS2。
Example 2
This example prepares MoS as follows2/C60The composite material comprises the following components:
(1) cutting carbon paper with area of 1 × 7cm, placing an alumina combustion boat containing 60.4mg of molybdenum trioxide powder in the center of a tube furnace, introducing argon gas into the upstream, and placing the carbon paper at the position of about 4cm away from the combustion boat in the downstream. At the beginning, argon is introduced for 30min to exhaust the air in the tube furnace, then the tube furnace is heated to 850 ℃ at the heating rate of 20 ℃/min under the protection of argon, the temperature is kept for 10min at the temperature, and finally the tube furnace is naturally cooled to the room temperature. This step allowed molybdenum trioxide to be deposited on the carbon paper.
(2) The combustion boat and the carbon paper were taken out of the tube furnace, the alumina combustion boat containing 400.4mg of sulfur powder was placed in the center of the tube furnace, argon gas was introduced upstream, and the carbon paper was placed downstream about 4cm from the combustion boat. At the beginning, argon is introduced for 30min to exhaust the air in the tube furnace, then the tube furnace is heated to 400 ℃ at the heating rate of 20 ℃/min under the protection of argon, the temperature is kept for 20min at the temperature, and finally the tube furnace is naturally cooled to the room temperature. This step converts the molybdenum trioxide on the carbon paper to molybdenum dioxide.
(3) And (3) weighing 400.4mg of sulfur powder to replace the sulfur powder in the step (2), and introducing argon for 30min to discharge the air in the tube furnace. Heating the tube furnace to 850 ℃ at the heating rate of 20 ℃/min under the protection of argon, preserving the heat for 20min at the temperature, and finally naturally cooling the tube furnace to room temperature to obtain the lamellar nano MoS deposited on the carbon paper2。
(4) 20mL of carbon tetrachloride solution was measured and poured into a beaker, and 10.4mg of fullerene (C) was weighed60) It was completely dissolved in carbon tetrachloride solution. Will deposit lamellar nano MoS2Soaking the carbon paper in the solution for 1min, taking out, and placing in a vacuum oven, first 120Drying for 4h, cooling to 80 ℃, drying for 12h, naturally cooling the vacuum oven to room temperature, and taking out a sample to obtain a target product: MoS deposited on carbon paper2/C60A composite material.
The characteristics show that the composite material obtained in the embodiment also takes the carbon paper as the substrate, a molybdenum disulfide sheet layered structure is formed on the carbon paper, and fullerene crystals are combined on the surface of the sheet layered molybdenum disulfide. And an antibacterial experiment shows that the composite material obtained in the embodiment also has good antibacterial 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 (10)
1. A preparation method of a molybdenum disulfide/fullerene semiconductor composite photocatalytic bactericide is characterized by comprising the following steps: the composite photocatalytic bactericide is obtained by synthesizing molybdenum disulfide on a carbon paper substrate and modifying the molybdenum disulfide by fullerene.
2. The preparation method according to claim 1, comprising the following steps:
(1) placing a combustion boat filled with molybdenum trioxide in the center of a tube furnace, placing carbon paper at the downstream, heating to 850 ℃ under the protection of argon atmosphere, keeping the temperature for 10min, and naturally cooling to room temperature to deposit molybdenum trioxide on the carbon paper;
(2) placing the combustion boat filled with sulfur powder in the center of a tube furnace, placing the carbon paper in the step 1 at the downstream, heating to 400 ℃ under the protection of argon atmosphere, preserving the heat for 20min, and naturally cooling to room temperature to convert molybdenum trioxide on the carbon paper into molybdenum dioxide;
(3) placing a combustion boat filled with sulfur powder with the same amount as the sulfur powder in the step 2 in the center of a tube furnace, placing the carbon paper in the step 2 at the downstream, heating to 850 ℃ under the protection of argon atmosphere, preserving the heat for 20min, and naturally cooling to room temperature to convert molybdenum dioxide on the carbon paper into molybdenum disulfide;
(4) and (3) dissolving fullerene powder in an organic solvent, then immersing the carbon paper obtained in the step (3) in the solution, taking out and drying to obtain the target product molybdenum disulfide/fullerene composite photocatalytic bactericide.
3. The method of claim 2, wherein: the fullerene is C60Or C70。
4. The method of claim 2, wherein: the mass ratio of the molybdenum trioxide in the step (1) to the sulfur powder in the step (2) is 1: 5-30.
5. The method of claim 2, wherein: the temperature increase rate in the steps (1) to (3) was 20 ℃/min.
6. The method of claim 2, wherein: in the step (4), the concentration of the fullerene powder in the organic solvent is 0.5-0.6 mg/mL.
7. The method of claim 2, wherein: in the step (4), the carbon paper is immersed in the solution for 1 min.
8. The method of claim 2, wherein: in the step (4), the drying is carried out in a vacuum oven at 120 ℃ for 4h, and then the temperature is reduced to 80 ℃ for 10-12 h.
9. The method of claim 2, wherein: in the step (4), the organic solvent is any one of carbon disulfide, carbon tetrachloride, p-xylene, o-xylene, m-trimethylbenzene, toluene, chlorobenzene and dichlorobenzene.
10. A molybdenum disulfide/fullerene semiconductor compound photocatalytic bactericide prepared by the preparation method of any one of claims 1 to 9.
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| YUN-HYUK CHOI，JONGBOK LEE，ABHISHEK PARIJA，等: "《An in Situ Sulfidation Approach for the Integration of MoS2 Nanosheets on Carbon Fiber Paper and the Modulation of Its Electrocatalytic Activity by Interfacing with nC60》", 《ACS CATALYSIS》 * |
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