CN113134370B - Ternary heterojunction photocatalysis antibacterial material and preparation method thereof - Google Patents
Ternary heterojunction photocatalysis antibacterial material and preparation method thereof Download PDFInfo
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- CN113134370B CN113134370B CN202110297413.0A CN202110297413A CN113134370B CN 113134370 B CN113134370 B CN 113134370B CN 202110297413 A CN202110297413 A CN 202110297413A CN 113134370 B CN113134370 B CN 113134370B
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- 239000000463 material Substances 0.000 title claims abstract description 54
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 44
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000007146 photocatalysis Methods 0.000 title claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229920001661 Chitosan Polymers 0.000 claims abstract description 39
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 18
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 239000006185 dispersion Substances 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 9
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 9
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 9
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
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- 238000000926 separation method Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 2
- 230000000845 anti-microbial effect Effects 0.000 claims 6
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- 238000005457 optimization Methods 0.000 description 8
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- 238000003756 stirring Methods 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
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- 239000001963 growth medium Substances 0.000 description 2
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 239000006137 Luria-Bertani broth Substances 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 229910000510 noble metal Inorganic materials 0.000 description 1
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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
-
- 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
- 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
- A01N59/02—Sulfur; Selenium; Tellurium; 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
- A01N59/26—Phosphorus; Compounds thereof
-
- B01J35/39—
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention relates to a ternary heterojunction photocatalytic antibacterial material and a preparation method thereof, wherein the material is a ternary heterojunction photocatalytic antibacterial material based on black phosphorus/polymer carbon quantum dots/molybdenum disulfide, and the preparation method comprises the following steps: dissolving chitosan in deionized water, adding NaOH, performing hydrothermal reaction, and performing centrifugal separation to obtain a supernatant which is a chitosan polymer carbon quantum dot solution; adding sodium molybdate and thiourea into deionized water respectively, adding polyvinylpyrrolidone, adding a chitosan polymer carbon quantum dot solution, and performing a hydrothermal reaction to obtain carbon quantum dot modified molybdenum disulfide; placing black phosphorus raw materials into absolute ethyl alcohol for ultrasonic dispersion to obtain black phosphorus dispersion liquid; and mixing the molybdenum disulfide modified by the carbon quantum dots with the black phosphorus dispersion liquid, and calcining to obtain the ternary heterojunction photocatalytic antibacterial material. The material prepared by the invention has high visible light utilization rate, low recombination rate of photo-generated electrons and holes, low cost and excellent photocatalytic antibacterial performance.
Description
Technical Field
The invention relates to the technical field of inorganic material synthesis, in particular to a ternary heterojunction photocatalytic antibacterial material and a preparation method thereof.
Background
The semiconductor photocatalytic material generates photo-generated electrons and holes (h) + ) Generates superoxide radical (O) under the condition of the participation of water and air 2- ) And hydroxyl radicals (. OH), etc. Reactive groups h produced in this process + 、·O 2- And OH, etc. can destroy the cell membrane of bacteria by oxidation, thereby causing leakage of constituent substances in the bacteriaThe dew finally deactivates the water-soluble antibacterial agent to achieve the aim of resisting bacteria. However, the conventional photocatalytic material has the defects of low visible light utilization rate, serious recombination of photo-generated electrons and holes and poor antibacterial effect. For example, conventional TiO 2 And the ZnO photocatalysis antibacterial material has low utilization rate of visible light, can only utilize a small part of ultraviolet light in sunlight, has serious photo-generated electron-hole pair recombination, and has poor antibacterial effect. The two-dimensional material has unique layered structure, high carrier mobility and remarkable in-plane anisotropic electronic properties. Wherein the two-dimensional black phosphorus has an adjustable band gap which can be adjusted from 0.3eV to 2.0eV by changing the layer number, and is further used together with a conventional photocatalyst (such as TiO 2 CdS and g-C 3 N 4 Etc.), black phosphorous nanoplatelets exhibit a broader and stronger light absorbing capacity in the visible and near infrared regions. Molybdenum disulfide (MoS) 2 ) Because of its low cost and high activity, it is often used as a promoter, and is considered to be the best choice for replacing noble metals. More importantly, moS 2 With a two-dimensional structure resembling black phosphorus, the two can combine to form a large contact interface, thereby providing adequate channels for photogenerated charge transfer. However, due to the recombination rate of Gao Guangsheng electrons and holes of the two materials, the photo-generated electrons and holes are seriously affected to exert an antibacterial effect.
Disclosure of Invention
The invention aims to solve the technical problems and the defects, and provides a ternary heterojunction photocatalytic antibacterial material and a preparation method thereof.
The invention solves the technical problems, and adopts the following technical scheme: a ternary heterojunction photocatalytic antibacterial material is based on black phosphorus/polymer carbon quantum dots/molybdenum disulfide.
A preparation method of a ternary heterojunction photocatalytic antibacterial material comprises the following steps:
firstly, taking chitosan raw materials, dissolving chitosan in deionized water, adding NaOH to form a chitosan aqueous solution, then adding the chitosan aqueous solution into a hydrothermal reaction kettle to perform hydrothermal reaction, after the reaction is completed, cooling to room temperature, and centrifugally separating to obtain a supernatant serving as a chitosan polymer carbon quantum dot solution for later use;
adding sodium molybdate and thiourea into deionized water respectively to form an aqueous solution, adding polyvinylpyrrolidone into the aqueous solution, adding the chitosan polymer carbon quantum dot solution obtained in the first step, performing hydrothermal reaction, standing to room temperature after the reaction is finished, centrifugally separating, washing with deionized water and absolute ethyl alcohol respectively, and drying to obtain carbon quantum dot modified molybdenum disulfide for later use;
thirdly, taking black phosphorus raw materials, placing the black phosphorus raw materials in absolute ethyl alcohol for ultrasonic dispersion, and obtaining black phosphorus dispersion liquid with different layers and band gaps by adjusting ultrasonic power and time for standby;
and step four, fully mixing the molybdenum disulfide modified by the carbon quantum dots obtained in the step two with the black phosphorus dispersion liquid obtained in the step three, drying under vacuum condition, and calcining under argon protection condition to obtain the ternary heterojunction photocatalytic antibacterial material based on the black phosphorus/polymer carbon quantum dots/molybdenum disulfide.
As a further optimization of the preparation method of the ternary heterojunction photocatalytic antibacterial material, in the first step, each 2g of chitosan is dissolved in 20-40ml of deionized water, and 0.01-0.1g of NaOH is added for hydrothermal reaction.
As a further optimization of the preparation method of the ternary heterojunction photocatalytic antibacterial material, the hydrothermal reaction condition in the first step is as follows: the reaction temperature is 150-250 ℃ and the reaction time is 20-30h.
As a further optimization of the preparation method of the ternary heterojunction photocatalytic antibacterial material, the centrifugal separation rotating speed is 6000-10000r/min, and the centrifugal separation time is 8-12min.
As a further optimization of the preparation method of the ternary heterojunction photocatalytic antibacterial material, the weight ratio of the sodium molybdate, the thiourea, the polyvinylpyrrolidone and the chitosan polymer carbon quantum dot solution is 10:7.5:1:10-20.
As a further optimization of the preparation method of the ternary heterojunction photocatalytic antibacterial material, the hydrothermal reaction condition in the second step is as follows: the reaction temperature is 200-260 ℃ and the reaction time is 20-30h.
As a further optimization of the preparation method of the ternary heterojunction photocatalytic antibacterial material, every 1g of black phosphorus raw material in the third step is placed in 60-100ml of absolute ethyl alcohol for ultrasonic dispersion.
As a further optimization of the preparation method of the ternary heterojunction photocatalytic antibacterial material, in the fourth step, each 1g of molybdenum disulfide modified by the carbon quantum dots obtained in the second step is mixed with 4ml of black phosphorus dispersion liquid obtained in the third step.
As a further optimization of the preparation method of the ternary heterojunction photocatalytic antibacterial material, the calcination temperature in the fourth step is 300-400 ℃ and the calcination time is 3-7h.
The invention has the following beneficial effects:
1. the invention utilizes black phosphorus and MoS 2 The two-dimensional structure of the material is modified by chitosan polymer carbon quantum dots, and the mobility of the photo-generated electrons and the mobility of the photo-generated holes in the material are further improved by utilizing the combination property of the chitosan polymer carbon quantum dots and two materials and the effect of conducting the photo-generated electrons and the photo-generated holes, so that the recombination of the photo-generated electrons and the photo-generated holes is inhibited, and the material with high visible light utilization rate, low photo-generated electron and hole recombination rate, low cost and excellent photo-catalytic antibacterial property is prepared.
2. The black phosphorus/polymer carbon quantum dot/molybdenum disulfide ternary heterojunction photocatalytic antibacterial material obtained by the invention is characterized by being capable of fully utilizing sunlight, effectively killing common bacteria under illumination conditions, having wide development prospect in the aspect of antibacterial materials, being capable of being used for modifying surfaces of medical equipment, antibacterial ceramics and the like and improving the antibacterial effect under illumination.
Drawings
FIG. 1 is a block diagram of a preparation process of a photocatalytic antibacterial material according to the present invention;
fig. 2 is a graph showing the antibacterial effect of the photocatalytic antibacterial material according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
A ternary heterojunction photocatalytic antibacterial material is based on black phosphorus/polymer carbon quantum dots/molybdenum disulfide.
Example 1
A preparation method of a ternary heterojunction photocatalytic antibacterial material comprises the following steps:
firstly, taking 2g of chitosan raw material, dissolving chitosan in 30ml of deionized water, adding 0.1g of NaOH, stirring and dissolving to form chitosan aqueous solution, then adding the chitosan aqueous solution into a 50ml of hydrothermal reaction kettle for hydrothermal reaction at 180 ℃ for 24 hours, after the reaction is completed, standing to room temperature, centrifuging, wherein the centrifuging speed is 8000r/min, and the centrifuging time is 10min, so that a supernatant liquid is the chitosan polymer carbon quantum dot solution for later use;
and step two, respectively adding 2g of sodium molybdate and 1.5g of thiourea into 30ml of deionized water to form an aqueous solution, adding 0.2g of polyvinylpyrrolidone into the aqueous solution, then adding 2ml of the chitosan polymer carbon quantum dot solution obtained in the step one, performing hydrothermal reaction at 220 ℃ for 24 hours, cooling to room temperature after the reaction is completed, centrifugally separating, respectively washing with deionized water and absolute ethyl alcohol for three times, and drying to obtain molybdenum disulfide modified by the carbon quantum dots for later use.
Example 2
Step three, taking 0.5g of block black phosphorus raw material, placing the block black phosphorus raw material in 40ml of absolute ethyl alcohol, and performing ultrasonic dispersion for 20min under the condition of 300W to obtain black phosphorus dispersion liquid for later use;
and step four, fully mixing 0.5g of the carbon quantum dot modified molybdenum disulfide obtained in the step two with 2ml of the black phosphorus dispersion liquid obtained in the step three, drying under vacuum condition, and calcining under argon protection condition at the calcining temperature of 350 ℃ for 5 hours to obtain the ternary heterojunction photocatalytic antibacterial material based on black phosphorus/polymer carbon quantum dot/molybdenum disulfide.
Example 3
To 30mL of deionized water, 2g of sodium molybdate, 0.2g of polyvinylpyrrolidone and 1.5g of thiourea were added, respectively, and the mixture was dissolved by stirring at room temperature. Transferring the obtained solution into a 50mL hydrothermal reaction kettle, maintaining at 220 ℃ for 24 hours, standing at room temperature, centrifuging, washing with deionized water and ethanol for three times respectively, and drying to obtain MoS 2 And (3) powder.
2mL of the black phosphorus dispersion obtained in example 2 and 0.5g of MoS were taken 2 And (3) fully mixing and grinding the powder, and calcining for 5 hours at 350 ℃ under the protection of Ar gas to obtain the black phosphorus/molybdenum disulfide binary heterojunction material.
Example 4
Colonies of staphylococcus aureus and escherichia coli are inoculated into 50mL of LB broth liquid culture medium respectively, the broth is placed into an incubator at 37 ℃ for culturing for 12 hours, a stock solution is obtained, and the concentration of the stock solution is calibrated to be 105CFU/mL by using sterile water.
0.2g of the samples obtained in examples 1, 2 and 3 (carbon quantum dot modified molybdenum disulfide, black phosphorus/polymer carbon quantum dot/molybdenum disulfide-based ternary heterojunction photocatalytic antibacterial material and black phosphorus/molybdenum disulfide binary heterojunction material) were dispersed in 10ml of dmso to prepare solutions to be tested, respectively. And respectively taking 100 mu L of the 2 original bacterial solutions prepared in the previous step, adding the 100 mu L of the 2 original bacterial solutions into 10mL of LB culture medium, preparing 6 groups of each bacterial solution of each solution to be tested, and arranging three groups of each bacterial solution in parallel, wherein one group is a blank group. After adding 10. Mu.L of the solution to be tested, culturing the solution under the illumination condition of 240rpm and 37 ℃ at the rotating speed, taking out one group of the solution at 0h, 2h, 4h, 6h and 8h, detecting the light absorption value in an ultraviolet spectrophotometer, and obtaining the growth curves of staphylococcus aureus and escherichia coli according to the detected absorbance (shown in figure 2).
Example 5
A preparation method of a ternary heterojunction photocatalytic antibacterial material comprises the following steps:
firstly, taking 2g of chitosan raw material, dissolving chitosan in 20ml of deionized water, adding 0.05g of NaOH, stirring and dissolving to form chitosan aqueous solution, then adding the chitosan aqueous solution into a 50ml of hydrothermal reaction kettle for hydrothermal reaction at a reaction temperature of 150 ℃ for 30 hours, after the reaction is completed, standing to room temperature, centrifuging, wherein the centrifuging speed is 6000r/min, the centrifuging time is 12min, and obtaining supernatant serving as chitosan polymer carbon quantum dot solution for later use;
and step two, respectively adding 2g of sodium molybdate and 1.5g of thiourea into 30ml of deionized water to form an aqueous solution, adding 0.2g of polyvinylpyrrolidone into the aqueous solution, then adding 2ml of the chitosan polymer carbon quantum dot solution obtained in the step one, performing hydrothermal reaction at the reaction temperature of 200 ℃ for 30 hours, standing to room temperature after the reaction is completed, centrifugally separating, respectively washing three times with deionized water and absolute ethyl alcohol, and drying to obtain the carbon quantum dot modified molybdenum disulfide for later use.
Step three, taking 0.5g of block black phosphorus raw material, placing the block black phosphorus raw material in 40ml of absolute ethyl alcohol, and performing ultrasonic dispersion for 20min under the condition of 300W to obtain black phosphorus dispersion liquid for later use;
and step four, fully mixing 0.5g of the carbon quantum dot modified molybdenum disulfide obtained in the step two with 2ml of the black phosphorus dispersion liquid obtained in the step three, drying under vacuum condition, calcining under argon protection condition, wherein the calcining temperature is 300 ℃, and the calcining time is 7 hours, so that the ternary heterojunction photocatalytic antibacterial material based on the black phosphorus/polymer carbon quantum dot/molybdenum disulfide is obtained.
Example 6
A preparation method of a ternary heterojunction photocatalytic antibacterial material comprises the following steps:
firstly, taking 2g of chitosan raw material, dissolving chitosan in 40ml of deionized water, adding 0.08g of NaOH, stirring and dissolving to form chitosan aqueous solution, then adding the chitosan aqueous solution into a 50ml of hydrothermal reaction kettle for hydrothermal reaction at a reaction temperature of 200 ℃ for 20 hours, after the reaction is completed, standing to room temperature, centrifuging, wherein the centrifuging speed is 10000r/min, and the centrifuging time is 8min, so that a supernatant liquid is the chitosan polymer carbon quantum dot solution for standby;
and step two, respectively adding 2g of sodium molybdate and 1.5g of thiourea into 30ml of deionized water to form an aqueous solution, adding 0.2g of polyvinylpyrrolidone into the aqueous solution, then adding 2ml of the chitosan polymer carbon quantum dot solution obtained in the step one, performing hydrothermal reaction at a reaction temperature of 260 ℃ for 20 hours, cooling to room temperature after the reaction is completed, centrifugally separating, respectively washing with deionized water and absolute ethyl alcohol for three times, and drying to obtain molybdenum disulfide modified by the carbon quantum dots for later use.
Step three, taking 0.5g of block black phosphorus raw material, placing the block black phosphorus raw material in 40ml of absolute ethyl alcohol, and performing ultrasonic dispersion for 20min under the condition of 300W to obtain black phosphorus dispersion liquid for later use;
and step four, fully mixing 0.5g of the carbon quantum dot modified molybdenum disulfide obtained in the step two with 2ml of the black phosphorus dispersion liquid obtained in the step three, drying under vacuum condition, calcining under argon protection condition at 400 ℃ for 3 hours to obtain the ternary heterojunction photocatalytic antibacterial material based on black phosphorus/polymer carbon quantum dot/molybdenum disulfide.
The foregoing describes specific embodiments of the present invention. It is to be understood that the invention is not limited to the particular embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the claims without affecting the spirit of the invention.
Claims (7)
1. A ternary heterojunction photocatalysis antibacterial material is characterized in that: the material is a ternary heterojunction photocatalytic antibacterial material based on black phosphorus/polymer carbon quantum dots/molybdenum disulfide, and the preparation method of the photocatalytic antibacterial material comprises the following steps: the method comprises the following steps:
firstly, taking chitosan raw materials, dissolving chitosan in deionized water, adding NaOH to form a chitosan aqueous solution, then adding the chitosan aqueous solution into a hydrothermal reaction kettle to perform hydrothermal reaction, after the reaction is completed, cooling to room temperature, and centrifugally separating to obtain a supernatant serving as a chitosan polymer carbon quantum dot solution for later use;
adding sodium molybdate and thiourea into deionized water respectively to form an aqueous solution, adding polyvinylpyrrolidone into the aqueous solution, adding the chitosan polymer carbon quantum dot solution obtained in the first step, performing hydrothermal reaction, standing to room temperature after the reaction is finished, centrifugally separating, washing with deionized water and absolute ethyl alcohol respectively, and drying to obtain molybdenum disulfide with a two-dimensional structure modified by carbon quantum dots for later use;
the weight ratio of the sodium molybdate, the thiourea, the polyvinylpyrrolidone and the chitosan polymer carbon quantum dot solution is 10:7.5:1:10-20 parts of a base;
thirdly, taking black phosphorus raw materials, placing the black phosphorus raw materials in absolute ethyl alcohol for ultrasonic dispersion, and obtaining black phosphorus dispersion liquid with different layers and band gaps by adjusting ultrasonic power and time for standby;
fully mixing the molybdenum disulfide modified by the carbon quantum dots obtained in the step two with the black phosphorus dispersion liquid obtained in the step three, drying under vacuum condition, and calcining under argon protection condition to obtain the ternary heterojunction photocatalytic antibacterial material based on the black phosphorus/polymer carbon quantum dots/molybdenum disulfide;
wherein, every 1g of molybdenum disulfide modified by the carbon quantum dots obtained in the second step is mixed with 4ml of black phosphorus dispersion liquid obtained in the third step.
2. A ternary heterojunction photocatalytic antimicrobial material as in claim 1, wherein: in the first step, each 2g of chitosan is dissolved in 20-40ml of deionized water, and 0.01-0.1g of NaOH is added for hydrothermal reaction.
3. A ternary heterojunction photocatalytic antimicrobial material as in claim 1, wherein: the hydrothermal reaction conditions in the first step are as follows: the reaction temperature is 150-250 ℃ and the reaction time is 20-30h.
4. A ternary heterojunction photocatalytic antimicrobial material as in claim 1, wherein: the centrifugal separation rotating speed is 6000-10000r/min, and the centrifugal separation time is 8-12min.
5. A ternary heterojunction photocatalytic antimicrobial material as in claim 1, wherein: the hydrothermal reaction conditions in the second step are as follows: the reaction temperature is 200-260 ℃ and the reaction time is 20-30h.
6. A ternary heterojunction photocatalytic antimicrobial material as in claim 1, wherein: in the third step, every 1g of black phosphorus raw material is placed in 60-100ml of absolute ethyl alcohol for ultrasonic dispersion.
7. A ternary heterojunction photocatalytic antimicrobial material as in claim 1, wherein: and step four, the calcination temperature is 300-400 ℃ and the calcination time is 3-7h.
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| CN113134370B true CN113134370B (en) | 2023-06-16 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106925310A (en) * | 2017-04-05 | 2017-07-07 | 中国科学技术大学先进技术研究院 | A kind of black phosphorus molybdenum disulfide nano elctro-catalyst and preparation method thereof, application |
| CN108745391A (en) * | 2018-05-24 | 2018-11-06 | 杭州电子科技大学 | A kind of New Two Dimensional black phosphorus nanometer sheet-MoS2Composite solar hydrogen manufacturing material and its preparation method and application |
| CN109292753A (en) * | 2018-12-06 | 2019-02-01 | 洛阳师范学院 | A kind of carbon quantum dot and its environment-friendly preparation method thereof and application |
| CN109433232A (en) * | 2018-11-21 | 2019-03-08 | 江苏大学 | The nonmetallic cocatalyst materials of ultra-thin black phosphorus alkene and preparation method and its composite material |
| CN112056310A (en) * | 2020-09-09 | 2020-12-11 | 陕西科技大学 | DFNS (double-walled carbon nanotubes) loaded carbon quantum dot/molybdenum disulfide quantum dot as well as preparation method and application thereof |
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| WO2016190531A1 (en) * | 2015-05-28 | 2016-12-01 | 한국표준과학연구원 | Method for preparing black phosphorus thin film and black phosphorus thin film prepared thereby |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106925310A (en) * | 2017-04-05 | 2017-07-07 | 中国科学技术大学先进技术研究院 | A kind of black phosphorus molybdenum disulfide nano elctro-catalyst and preparation method thereof, application |
| CN108745391A (en) * | 2018-05-24 | 2018-11-06 | 杭州电子科技大学 | A kind of New Two Dimensional black phosphorus nanometer sheet-MoS2Composite solar hydrogen manufacturing material and its preparation method and application |
| CN109433232A (en) * | 2018-11-21 | 2019-03-08 | 江苏大学 | The nonmetallic cocatalyst materials of ultra-thin black phosphorus alkene and preparation method and its composite material |
| CN109292753A (en) * | 2018-12-06 | 2019-02-01 | 洛阳师范学院 | A kind of carbon quantum dot and its environment-friendly preparation method thereof and application |
| CN112056310A (en) * | 2020-09-09 | 2020-12-11 | 陕西科技大学 | DFNS (double-walled carbon nanotubes) loaded carbon quantum dot/molybdenum disulfide quantum dot as well as preparation method and application thereof |
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