CN111203247A - Red phosphorus-based semiconductor antibacterial photocatalyst and preparation method thereof - Google Patents
Red phosphorus-based semiconductor antibacterial photocatalyst and preparation method thereof Download PDFInfo
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 59
- 239000004065 semiconductor Substances 0.000 title claims abstract description 33
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 35
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 19
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 16
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 10
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract description 10
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001936 tantalum oxide Inorganic materials 0.000 claims abstract description 9
- 239000011787 zinc oxide Substances 0.000 claims abstract description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001308 Zinc ferrite Inorganic materials 0.000 claims abstract description 3
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 claims abstract description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 3
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 10
- 239000004570 mortar (masonry) Substances 0.000 claims description 10
- 239000010453 quartz Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 238000001228 spectrum Methods 0.000 abstract 1
- 230000001580 bacterial effect Effects 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000000725 suspension Substances 0.000 description 14
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- 241000233866 Fungi Species 0.000 description 9
- 241000228197 Aspergillus flavus Species 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000010790 dilution Methods 0.000 description 6
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- 239000007787 solid Substances 0.000 description 6
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- 241000894006 Bacteria Species 0.000 description 4
- 241000588724 Escherichia coli Species 0.000 description 4
- 241000191967 Staphylococcus aureus Species 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 239000002071 nanotube Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 241000228245 Aspergillus niger Species 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000002538 fungal effect Effects 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 2
- 241000191940 Staphylococcus Species 0.000 description 2
- 241000191963 Staphylococcus epidermidis Species 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- 230000000941 anti-staphylcoccal effect Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- -1 diluting by times Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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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
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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
- A01N59/26—Phosphorus; Compounds thereof
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- 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
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- A61L9/20—Ultraviolet radiation
- A61L9/205—Ultraviolet radiation using a photocatalyst or photosensitiser
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Abstract
The invention discloses a red phosphorus-based semiconductor antibacterial photocatalyst and a preparation method thereof, wherein red phosphorus and a semiconductor, such as titanium oxide, zinc oxide, iron oxide, tantalum oxide, tungsten oxide, bismuth vanadate, bismuth tungstate, bismuth molybdate, bismuth ferrite, zinc ferrite, carbon nitride and the like, are uniformly mixed by adopting two processes of high-temperature roasting and grinding respectively to form the red phosphorus/semiconductor composite photocatalyst. The spectrum absorption range of the composite material is expanded to the whole visible light region, so that the optical absorption is improved, the effective separation and transmission of photo-generated charges are promoted, the photocatalytic antibacterial performance of the material is improved, and in addition, the preparation method is simple and easy to industrialize.
Description
Technical Field
The invention belongs to the field of preparation and application of antibacterial materials, and particularly relates to a red phosphorus-based semiconductor antibacterial photocatalyst and a preparation method thereof.
Background
With the rapid development of society, a large amount of harmful microorganisms such as bacteria and fungi exist in the living environment (such as drinking water and air), and the propagation of the harmful microorganisms can seriously affect the body health. Nowadays, the emerging photocatalytic sterilization technology has gradually replaced the traditional purification technology such as ultraviolet, chloride or ozone sterilization. Research shows that the photocatalytic antibacterial material has excellent sterilizing and antibacterial performance, can kill various microbes and has no secondary pollution to environment. Therefore, the antibacterial photocatalyst has good application prospect in the fields of water purification and air purification. At present, anatase TiO2The photocatalyst antibacterial material is known to be the most widely applied photocatalytic antibacterial material due to low price, easy obtaining, no toxicity, no harm, stable chemical property and strong light corrosion resistance. However, the defects of wide optical band gap, easy recombination of photo-generated charges and the like cause the low photocatalytic activity, thereby restricting the practical application of the photocatalyst in photocatalysis antibiosis. Therefore, how to improve the utilization efficiency of light, promote charge separation and construct a semiconductor photocatalyst with visible light response has practical application value.
Disclosure of Invention
The invention aims to solve the technical problem of providing a red phosphorus-based semiconductor antibacterial photocatalyst and a preparation method thereof aiming at the defects of the prior art. The prepared red phosphorus-based semiconductor photocatalyst shows excellent and rapid antibacterial performance.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a red phosphorus-based semiconductor antibacterial photocatalyst comprises the following steps:
1) preparing the red phosphorus/semiconductor composite photocatalyst by a ball milling method: uniformly grinding a certain mass of semiconductor and red phosphorus in a mortar, then placing the mixture in a ball mill, and carrying out ball milling for 2-24 h at the rotating speed of 600 revolutions per minute under the protective atmosphere of argon or nitrogen, thus obtaining the red phosphorus/semiconductor composite photocatalyst A, wherein the mass ratio of the semiconductor to the red phosphorus is (1: 0.1) - (1: 0.5);
or 2) preparing the red phosphorus/semiconductor composite photocatalyst by a quartz tube vacuum high-temperature roasting method: uniformly grinding a certain mass of semiconductor and red phosphorus in a mortar, then placing the mixture in a quartz tube, vacuumizing, sealing the quartz tube, and roasting at 400-800 ℃ for 2-5 hours to obtain the red phosphorus/semiconductor composite photocatalyst B, wherein the mass ratio of the semiconductor to the red phosphorus is (1: 0.1) - (1: 0.5);
the semiconductor comprises one or more of titanium oxide, zinc oxide, iron oxide, tantalum oxide, tungsten oxide, bismuth vanadate, bismuth tungstate, bismuth molybdate, bismuth ferrite, zinc ferrite and carbon nitride.
The application of the red phosphorus-based semiconductor photocatalyst prepared by the method in the antibacterial field is as follows:
1) water body antibiosis: the method comprises the steps of dispersing a certain mass of photocatalyst into an aqueous solution containing bacteria (escherichia coli, staphylococcus albus, staphylococcus aureus and the like) or fungi (aspergillus flavus, aspergillus niger and the like), and using a xenon lamp to simulate sunlight and visible light, white light LED visible light and blue light, green light and red light LED lamps with different wave bands for irradiation. And (3) after a certain time of illumination, taking out the bacterial suspension, diluting by times, coating the diluted bacterial suspension on a solid culture medium, culturing, counting, and calculating the sterilization rate.
2) Air antibiosis: coating a certain mass of photocatalyst on a porous panel, placing the porous panel in a closed test cabinet, presetting bacteria (escherichia coli, staphylococcus albus, staphylococcus aureus and the like) or fungi (aspergillus flavus, aspergillus niger and the like) in the test cabinet, and using a xenon lamp to simulate sunlight and visible light, white light LED visible light and blue light, green light and red light LED lamps with different wave bands for irradiation. After a certain time of illumination, sampling by using a liquid impact type microorganism aerosol sampler, culturing and counting, and calculating the sterilization rate.
The invention has the beneficial effects that: the red phosphorus responsive to visible light is compounded with the semiconductor, so that the spectral absorption range of the composite material is expanded to the whole visible light region, the optical absorption is improved, the effective separation and transmission of photo-generated charges are promoted, the photocatalytic antibacterial performance of the material is improved, and in addition, the preparation method is simple and easy to industrialize.
Drawings
FIG. 1 is a curve of anti-Escherichia coli performance in water of the red phosphorus/titanium oxide composite photocatalyst obtained in example 1 of the present invention.
FIG. 2 is a graph showing the anti-Staphylococcus aureus performance of the red phosphorus/zinc oxide composite photocatalyst obtained in example 2 of the present invention in water.
Fig. 3 is a performance curve of anti-aspergillus flavus in a water body of the red phosphorus/tantalum oxide composite photocatalyst obtained in the embodiment 3 of the invention.
FIG. 4 is a graph showing the performance of anti-Staphylococcus albus in air of the red phosphorus/carbon nitride composite photocatalyst obtained in example 4 of the present invention.
Fig. 5 is a performance curve of the red phosphorus/carbon nitride composite photocatalyst against aspergillus flavus in a water body obtained in example 5 of the present invention.
FIG. 6 is a curve of anti-Aspergillus flavus performance in water of the red phosphorus/bismuth tungstate composite photocatalyst obtained in example 6 of the present invention.
Detailed Description
The invention is further illustrated with reference to the following figures and examples.
Example 1
A preparation method of a red phosphorus/titanium oxide composite photocatalyst comprises the following steps:
200mg of commercially available P25 titanium oxide powder and 50mg of red phosphorus are uniformly ground in a mortar; the mixture was then encapsulated in a quartz tube and fired at 600 ℃ for 4 h. Thus obtaining the red phosphorus/titanium oxide composite photocatalyst.
The antibacterial performance of the red phosphorus/titanium oxide composite photocatalyst in water is tested:
50mg of red phosphorus/titanium oxide photocatalyst was dispersed in 50mL of a solution containing the red phosphorus/titanium oxide photocatalyst at a concentration of 2.9X 106cfu/mL Escherichia coli in an aqueous solution at 20mW/cm2The xenon lamp with light intensity simulates sunlight for irradiation. During the reaction, 1mL of the solution was taken out of the reactor every 20min, and the taken-out bacterial suspensions were doubled in sequence in a clean benchSpecific dilution of several gradients (10)-1～10-5) Then, 100. mu.L of the bacterial suspension was taken out from the bacterial suspension at different dilution times and spread on a solid LB medium. The plate was placed upside down in an electric incubator at 37 ℃ for 24 hours. After the culture is finished, counting the number of bacterial colonies by adopting a plate counting method, and calculating the bacterial inactivation rate, as shown in figure 1.
Under the irradiation of simulated sunlight of a xenon lamp, the escherichia coli in the water body can be quickly eliminated within 60 min. The catalyst can generate a photogenerated electron with reducibility and a photogenerated hole with oxidizability under the illumination condition. Wherein the photo-generated electrons react with oxygen to generate a large number of active superoxide radicals, the photo-generated holes react with water to generate a large number of hydroxyl radicals, and the photo-generated holes have strong oxidizing property. These active species can effectively destroy the bacterial cell wall, achieving the purpose of killing bacteria.
Example 2
A preparation method of a red phosphorus/zinc oxide composite photocatalyst comprises the following steps:
grinding 200mg of commercially available zinc oxide powder and 60mg of red phosphorus uniformly in a mortar; and then ball-milling for 12 hours at the rotating speed of 400 r/min under the protection atmosphere of argon or nitrogen. Thus obtaining the RP/zinc oxide composite photocatalyst.
And (3) testing the antibacterial performance of the red phosphorus/zinc oxide composite photocatalyst:
dispersing a certain mass of red phosphorus/zinc oxide photocatalyst in a solution containing the red phosphorus/zinc oxide photocatalyst with the concentration of 6.5 multiplied by 10620mW/cm of cfu/mL staphylococcus aureus water solution2The white light LED with light intensity irradiates. During the reaction, 1mL of the solution was withdrawn from the reactor every 20min, and the withdrawn bacterial suspension was sequentially diluted in multiple steps (10) in a super clean bench-1～10-5) Then, 100. mu.L of the bacterial suspension was taken out from the bacterial suspension at different dilution times and spread on a solid LB medium. The plate was placed upside down in an electric incubator at 37 ℃ for 24 hours. After the culture is finished, counting the number of bacterial colonies by adopting a plate counting method, and calculating the bacterial inactivation rate, as shown in figure 2.
Under the irradiation of white light LED visible light, the staphylococcus aureus in the water body can be quickly eliminated within 60 min.
Example 3
A preparation method of a red phosphorus/tantalum oxide composite photocatalyst comprises the following steps:
grinding 200mg of commercially available tantalum oxide powder and 40mg of red phosphorus uniformly in a mortar; the mixture was packed in a quartz tube and fired at 500 ℃ for 5 h. Thus obtaining the red phosphorus/tantalum oxide composite photocatalyst.
And (3) testing the antibacterial performance of the red phosphorus/tantalum oxide composite photocatalyst:
dispersing a certain mass of red phosphorus/tantalum oxide photocatalyst in a solution containing 2.5 × 105cfu/mL of an aqueous solution of Aspergillus flavus at 20mW/cm2The blue LED with light intensity irradiates. During the reaction, 1mL of the solution was withdrawn from the reactor, and the withdrawn fungal suspension was diluted several gradients in multiple ratios in sequence in a clean bench (10)-1～10-5) Then, 100. mu.L of bacterial suspension at different dilution was dropped onto the prepared solid PDA medium. The plates were incubated in an electric incubator at 30 ℃ for 4 days. And after the culture is finished, counting the number of fungus colonies by adopting a plate counting method, and calculating the fungus inactivation rate.
Under the irradiation of blue light LED visible light, aspergillus flavus in the water body can be quickly eliminated within 60 min.
Example 4
A preparation method of a red phosphorus/carbon nitride composite photocatalyst comprises the following steps:
2g of melamine and urea (mass ratio is 1:10) are taken out of a muffle furnace, the heating rate is 3 ℃/min, and the mixture is roasted for 3h at 550 ℃ to obtain the carbon nitride nanotube.
Grinding 200mg of carbon nitride nanotube powder and 40mg of red phosphorus uniformly in a mortar; the mixture was packed in a quartz tube and calcined at 450 ℃ for 3 h. Thus obtaining the red phosphorus/carbon nitride composite photocatalyst.
And (3) testing the antibacterial performance of the red phosphorus/carbon nitride composite photocatalyst:
coating a certain mass of red phosphorus/carbon nitride photocatalyst on a porous panel, and placing the porous panel on1m3In the closed test cabinet, 2.2 is multiplied by 10 in advance6cfu/m3The white staphylococcus of (4) is used with the concentration of 20mW/cm2The blue LED with light intensity irradiates. In the reaction process, a liquid impact type microorganism aerosol sampler is used for sampling, culture counting is carried out, and the inactivation rate is calculated.
Under the irradiation of blue light LED visible light, the white staphylococcus in the air can be quickly eliminated within 120 min.
Example 5
A preparation method of a red phosphorus/carbon nitride composite photocatalyst comprises the following steps:
2g of melamine and urea (mass ratio is 1:10) are taken out of a muffle furnace, the heating rate is 3 ℃/min, and the mixture is roasted for 3h at 550 ℃ to obtain the carbon nitride nanotube.
Grinding 200mg of carbon nitride nanotube powder and 50mg of red phosphorus uniformly in a mortar; the mixture was packed in a quartz tube and fired at 500 ℃ for 4 h. Thus obtaining the red phosphorus/carbon nitride composite photocatalyst.
And (3) testing the antibacterial performance of the red phosphorus/carbon nitride composite photocatalyst:
dispersing a certain mass of red phosphorus/carbon nitride photocatalyst in a solution containing 2 x 10 of red phosphorus/carbon nitride photocatalyst5cfu/mL of an aqueous solution of Aspergillus flavus at 20mW/cm2The white light LED with light intensity irradiates. During the reaction, 1mL of the solution was withdrawn from the reactor, and the withdrawn fungal suspension was diluted several gradients in multiple ratios in sequence in a clean bench (10)-1～10-5) Then, 100. mu.L of bacterial suspension at different dilution was dropped onto the prepared solid PDA medium. The plates were incubated in an electric incubator at 30 ℃ for 4 days. And after the culture is finished, counting the number of fungus colonies by adopting a plate counting method, and calculating the fungus inactivation rate.
Under the irradiation of white light LED visible light, aspergillus flavus in the water body can be quickly eliminated within 40 min.
Example 6
A preparation method of a red phosphorus/bismuth tungstate composite photocatalyst comprises the following steps:
grinding 200mg of commercially available bismuth tungstate and 100mg of red phosphorus uniformly in a mortar; then ball milling is carried out for 16h under the protection atmosphere of argon or nitrogen at the rotating speed of 500 r/min. . Thus obtaining the red phosphorus/bismuth tungstate composite photocatalyst.
And (3) testing the antibacterial performance of the red phosphorus/bismuth tungstate composite photocatalyst:
dispersing a certain mass of red phosphorus/bismuth tungstate photocatalyst in a solution containing 3 x 10 of red phosphorus/bismuth tungstate5cfu/mL of Aspergillus niger aqueous solution at 20mW/cm2The blue LED with light intensity irradiates. During the reaction, 1mL of the solution was withdrawn from the reactor, and the withdrawn fungal suspension was diluted several gradients in multiple ratios in sequence in a clean bench (10)-1～10-5) Then, 100. mu.L of bacterial suspension at different dilution was dropped onto the prepared solid PDA medium. The plates were incubated in an electric incubator at 30 ℃ for 4 days. And after the culture is finished, counting the number of fungus colonies by adopting a plate counting method, and calculating the fungus inactivation rate. Under the irradiation of blue light LED visible light, aspergillus flavus in the water body can be quickly eliminated within 80 min.
Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the invention, and it should be understood by those skilled in the art that various modifications and variations can be made without inventive faculty, based on the technical solutions of the present invention.
Claims (2)
1. A preparation method of a red phosphorus-based semiconductor antibacterial photocatalyst is characterized by comprising the following steps:
1) preparing the red phosphorus/semiconductor composite photocatalyst by a ball milling method: uniformly grinding a certain mass of semiconductor and red phosphorus in a mortar, then placing the mixture in a ball mill, and carrying out ball milling for 2-24 h at the rotating speed of 600 revolutions per minute under the protective atmosphere of argon or nitrogen, thus obtaining the red phosphorus/semiconductor composite photocatalyst A, wherein the mass ratio of the semiconductor to the red phosphorus is (1: 0.1) - (1: 0.5);
or 2) preparing the red phosphorus/semiconductor composite photocatalyst by a quartz tube vacuum high-temperature roasting method: uniformly grinding a certain mass of semiconductor and red phosphorus in a mortar, then placing the mixture in a quartz tube, vacuumizing, sealing the quartz tube, and roasting at 400-800 ℃ for 2-5 hours to obtain the red phosphorus/semiconductor composite photocatalyst B, wherein the mass ratio of the semiconductor to the red phosphorus is (1: 0.1) - (1: 0.5);
the semiconductor comprises one or more of titanium oxide, zinc oxide, iron oxide, tantalum oxide, tungsten oxide, bismuth vanadate, bismuth tungstate, bismuth molybdate, bismuth ferrite, zinc ferrite and carbon nitride.
2. A red phosphorus-based semiconductor antibacterial photocatalyst prepared by the method for preparing a red phosphorus-based semiconductor antibacterial photocatalyst according to claim 1.
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