CN113546665A - Composite photocatalytic film for inhibiting growth of harmful microalgae and preparation method and application thereof - Google Patents
Composite photocatalytic film for inhibiting growth of harmful microalgae and preparation method and application thereof Download PDFInfo
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 230000012010 growth Effects 0.000 title claims abstract description 28
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
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- 238000000034 method Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- YSRVJVDFHZYRPA-UHFFFAOYSA-N melem Chemical compound NC1=NC(N23)=NC(N)=NC2=NC(N)=NC3=N1 YSRVJVDFHZYRPA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 241000192710 Microcystis aeruginosa Species 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 12
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000004132 cross linking Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- 238000002791 soaking Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 16
- 229920002301 cellulose acetate Polymers 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 241000290272 Karenia mikimotoi Species 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 4
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- 229910052573 porcelain Inorganic materials 0.000 description 9
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 8
- 238000007605 air drying Methods 0.000 description 7
- 229910021642 ultra pure water Inorganic materials 0.000 description 7
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- 229920000877 Melamine resin Polymers 0.000 description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
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- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
- B01J31/0247—Imides, amides or imidates (R-C=NR(OR))
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The application belongs to the technical field of water bloom pollution treatment, and particularly relates to a composite photocatalytic film for inhibiting growth of harmful microalgae, and a preparation method and application thereof. The application provides a preparation method of a composite photocatalytic film capable of stably floating on water surface and inhibiting growth of harmful microalgae, which comprises the following steps: step 1, mixing melem and pyromellitic anhydride, and calcining to prepare pyromellitic anhydride modified graphite-phase carbon nitride powder; step 2, crosslinking and mixing pyromellitic anhydride modified graphite-phase carbon nitride powder, a crosslinking agent and an organic solvent to prepare a crosslinked substance; and 3, coating or soaking the cross-linked substance on a substrate, and drying until the film of the substrate falls off to obtain the composite photocatalytic film for inhibiting the growth of harmful microalgae. The application provides a composite photocatalytic film for inhibiting harmful microalgae growth and a preparation method and application thereof, and effectively solves the problems of time and labor waste and difficult material recovery in the existing method for treating harmful microalgae.
Description
Technical Field
The application belongs to the technical field of water bloom pollution treatment, and particularly relates to a composite photocatalytic film for inhibiting growth of harmful microalgae, and a preparation method and application thereof.
Background
In recent years, with the rapid development of industry, various water bodies such as oceans, lakes, reservoirs and the like are increasingly polluted, and water eutrophication is one of the main water pollution problems. The eutrophication of the water body leads algae and other plankton to grow rapidly, the water body deteriorates, the fishes and other organisms die in a large quantity, and the algae proliferate explosively and generate water bloom in the late eutrophication period. The water bloom reduces the content of dissolved oxygen in water, a large number of animals and phytoplankton in the water die, the water body becomes smelly, and the water quality deterioration is aggravated. Currently, the removal techniques for algae mainly include physical, chemical and biological methods. The conventional chemical reagents of chlorine dioxide, potassium permanganate and ozone can inhibit the growth of algae; the algae can be removed by ultrasonic wave, mechanical fishing, dilution scouring and flocculation sedimentation; biological algae removal technology is also widely used because of its environmentally friendly nature. However, these methods have some problems. The added chemical algaecide is easy to cause secondary pollution, the physical method needs larger manpower and material resource investment, and the biological method is easy to interfere biological diversity. Therefore, a more environmentally friendly, inexpensive and sustainable algae inhibition technology is urgently needed.
Disclosure of Invention
Based on the above, the application provides a composite photocatalytic film for inhibiting the growth of harmful microalgae, and a preparation method and an application thereof, and effectively solves the problems of time and labor waste and difficult material recovery in the existing method for treating the harmful microalgae.
The application provides a preparation method of a composite photocatalytic film for inhibiting growth of harmful microalgae, which comprises the following steps:
and 3, coating or soaking the cross-linked substance on a substrate, and drying until the film of the substrate falls off to obtain the composite photocatalytic film for inhibiting the growth of harmful microalgae.
Specifically, the preparation method of the Melem comprises the following steps: placing melamine in an alumina crucible, heating to 400-440 ℃ at a heating rate of 3-5 ℃/min, keeping the temperature, continuing to heat for 8-9 h, preparing Melem powder, suspending the Melem powder in 100 ℃ ultrapure water for 3h, then carrying out vacuum filtration on the filtered liquid, placing the obtained solid in an oven, and drying to obtain the Melamine Melem.
In another embodiment, the mass ratio of the melem to the pyromellitic anhydride is (0.5-2.0): 1.
Specifically, the mass ratio of the melem to the pyromellitic dianhydride PMDA is 1: 1.
In another embodiment, in the step 1, the calcination temperature is 300-330 ℃, the calcination heating rate is 6-7 ℃/min, and the calcination time is 3-4 h.
In another embodiment, the cross-linking agent is selected from cellulose acetate or/and polystyrene.
In another embodiment, the organic solvent is selected from acetone or/and dimethylformamide.
In another embodiment, the ratio of the pyromellitic anhydride-modified graphite-phase carbon nitride powder to the crosslinking agent to the organic solvent is (0.5 to 1.1) g: 1 g: 15 mL.
In another embodiment, the substrate is selected from a glass sheet, a stainless steel sheet, or a silicon sheet.
In another embodiment, in the step 2, the mixing is ultrasonic mixing, and the mixing time is 3 to 5 hours.
In another embodiment, in step 3, the drying is air drying at room temperature.
The second aspect of the application provides a composite photocatalytic film for inhibiting the growth of harmful microalgae, which comprises the composite photocatalytic film prepared by the preparation method; the composite photocatalytic film can stably float on the water surface.
The third aspect of the application discloses the application of the composite photocatalytic film prepared by the preparation method in inhibiting the growth of harmful microalgae.
In another embodiment, the method comprises the following steps: the composite photocatalytic film prepared by the preparation method floats on the water surface containing harmful microalgae, and the growth of the harmful microalgae is inhibited under natural illumination.
In another embodiment, the harmful microalgae has a density of 5 × 104～11×106cells/mL; the harmful microalgae are selected from one or more of microcystis aeruginosa, Karenia mikimotoi and Chroococcum micranthum.
Compared with the traditional algae removal method in which the powder algae removal agent is added once, the composite photocatalytic film is a floating photocatalytic film, and has the advantages of convenience in material recovery, repeated recycling and no secondary pollution.
The precursor prepared by calcining melamine and pyromellitic dianhydride (PMDA) are uniformly mixed and then are prepared into a composite photocatalytic film (g-C) capable of floating on water surface through a crosslinking reaction3N4a/PDI membrane); wherein the graphite phase carbon nitride (g-C)3N4) Has proper band gap width, is a layered non-metal semiconductor photocatalyst, and prepares g-C by calcination for improving the photocatalytic efficiency3N4The photocatalytic efficiency of the PDI powdery photocatalyst is obviously improved. g-C prepared in this application3N4the/PDI film can float on the surface of a water body containing harmful microalgae, and g-C is obtained under the illumination of natural light3N4the/PDI membrane can inhibit the growth of microalgae, and the g-C of the application3N4the/PDI membrane can be recovered by salvaging, is easy to recover, and can recover g-C3N4After the PDI membrane, harmful microalgae in the water body do not continue to grow, and the method is environment-friendly; and g-C of the present application3N4the/PDI membrane has stable structure, can be recycled after being salvaged from a water body, and has good application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 provides g-C for example 1 of the present application3N4A real map and a test map of the/PDI membrane;
FIG. 2 provides the use of g-C for the examples of the present application3N4PDI membranes and the absence of g-C3N4A plot of the algae inhibition efficiency of the PDI membrane to microcystis aeruginosa in sunlight;
FIG. 3 shows g-C provided for comparative examples of the present application3N4The algae inhibiting efficiency of the membrane to microcystis aeruginosa under sunlight is shown.
Detailed Description
The application provides a composite photocatalytic film for inhibiting harmful microalgae growth, and a preparation method and application thereof, which are used for solving the technical defects of time and labor waste and difficult material recovery in the method for treating the harmful microalgae in the prior art.
The technical solutions in the embodiments of the present application will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The raw materials and reagents used in the following examples are commercially available or self-made.
Example 1
The embodiment of the application provides a method for inhibiting growth of harmful microalgae by using a composite photocatalytic film, which comprises the following steps:
1. preparation of g-C3N4(PDI) photocatalyst powder:
10g of melamine is placed in an alumina crucible, heated to 425 ℃ at the heating rate of 3 ℃/min, and then kept at the temperature for heating for 9 hours, thus preparing the precursor Melem. The Melem powder was suspended in ultrapure water at 100 ℃ for 3h, then filtered with the aid of a vacuum filter and the solid obtained was dried in an oven. The dried Melem powder was mixed homogeneously with PMDA in the same mass ratio.Putting the mixed mixture into a porcelain crucible with a cover, covering the porcelain crucible with the cover, putting the porcelain crucible into a muffle furnace again, heating to 325 ℃ at a heating rate of 7 ℃/min, calcining for 4h at 325 ℃, and then obtaining g-C3N4A/PDI powder.
2. G to C3N4Mixing PDI powder, an organic cross-linking agent and an organic solvent by an ultrasonic method, pouring the mixture on a substrate, and then air-drying to form a film:
1g of Cellulose Acetate (CA) powder, and 1.1g of g-C prepared as described above were weighed3N4A/PDI powder. 15mL of acetone was measured into a 50mL beaker and the CA powder was added slowly while shaking slightly to speed up dissolution. After the CA is dissolved in a large amount, g-C is slowly added3N4The powder was shaken up with shaking. And (4) performing ultrasonic treatment for 2h, adding 2mL of hot ultrapure water, and continuing ultrasonic treatment for 1 h. And (3) transferring 2.4mL of liquid into a 6cm glass culture dish by using a liquid transfer gun while the liquid is hot, shaking the culture dish to uniformly disperse, and air-drying the culture dish in a fume hood for 1.5 hours to obtain the composite photocatalytic film. The object of the composite photocatalytic film provided by the embodiment of the application is shown in the left picture of fig. 1.
3. As shown in the right diagram of fig. 1, the obtained composite photocatalytic film floats in the water solution containing harmful microalgae, and the simulated natural light source is turned on to realize the growth inhibition of the harmful microalgae:
microcystis aeruginosa (Microcystis aeruginosa) is selected as the algae species for inhibiting algae. The concentration is selected to be about 10X 106cells/mL, 35mL of the algal solution was put in a 100mL beaker. Two parts of the same algae liquid are taken, one part is put into the prepared composite photocatalytic film, and the other part is a light control (marked with no film) without the composite photocatalytic film. Culturing the two algae solutions in a light incubator at 23 + -2 deg.C for 12h with a light-dark ratio of 12h to 12h and a light intensity of 2000Lux for 5 days. The absorbance of the algal solution was measured by sampling at 0, 0.5 (dark control), 1, 2, 3, 4, and 5 days, and the concentration change of the algal solution was characterized, and the results are shown in FIG. 2. As can be seen from FIG. 2, the added composite photocatalytic film has an obvious effect of inhibiting the growth of Microcystis aeruginosa, compared with the algae sample without the added composite photocatalytic film. Removing the composite photocatalytic film after the composite photocatalytic film is treated for two days, and removing the verdigris microorganismThe growth of the spirulina is not restored, and the density is continuously reduced, which indicates that the composite photocatalytic film of the application has irreversible damage to the spirulina cells. The result shows that the composite photocatalytic film can obviously inhibit the growth of microcystis aeruginosa.
Example 2
The embodiment of the application provides a method for inhibiting harmful algae growth by using a composite photocatalytic film, which comprises the following steps:
1. preparation of g-C3N4(PDI) photocatalyst powder:
5g of melamine is placed in an alumina crucible, heated to 425 ℃ at the heating rate of 3 ℃/min, and then kept at the temperature for heating for 8 hours, thus preparing the precursor Melem. The Melem powder was suspended in ultrapure water at 100 ℃ for 4h and then filtered by means of a vacuum filter, and the resulting solid was dried in an oven. The dried Melem powder was mixed homogeneously with PMDA in the same mass ratio. Putting the mixed mixture into a porcelain crucible with a cover, covering the porcelain crucible with the cover, putting the porcelain crucible into a muffle furnace again, heating to 325 ℃ at a heating rate of 7 ℃/min, calcining for 3h at 325 ℃, and then obtaining g-C3N4A/PDI powder.
2. G to C3N4Mixing PDI powder, an organic cross-linking agent and an organic solvent by an ultrasonic method, pouring the mixture on a substrate, and then air-drying to form a film:
1g of polystyrene powder, and 0.8g of g-C prepared above were weighed3N4A/PDI powder. 15mL of acetone was measured into a 50mL beaker and polystyrene powder was added slowly while accelerating dissolution with gentle shaking. After it has dissolved in a large amount, g-C is slowly added3N4The powder was shaken up with shaking. And (4) performing ultrasonic treatment for 3h, adding 2mL of hot ultrapure water, and continuing ultrasonic treatment for 1 h. And (3) transferring 2.4mL of liquid onto a 6cm silicon chip by using a liquid transfer gun while the liquid is hot, shaking to uniformly disperse the liquid, and air-drying the liquid for 2 hours in a fume hood to obtain the composite photocatalytic film.
3. The obtained composite photocatalytic film floats in a water solution containing harmful microalgae, and a simulated natural light source is turned on to realize growth inhibition on the harmful microalgae:
selecting Chroococcus minutus as a target algae inhibiting algae species. The concentration is selected to be about 4 × 106cells/mL, 35mL of the algal solution was put in a 100mL beaker. Taking two parts of the same algae liquid, putting one part of the algae liquid into the prepared composite photocatalytic film, and putting the other part of the algae liquid into the prepared composite photocatalytic film as light contrast without the composite photocatalytic film. Culturing the two algae solutions in a light incubator at 23 + -2 deg.C for 12h with a light-dark ratio of 12h to 12h and a light intensity of 2000Lux for 5 days. Samples were taken at 0, 0.5 (dark control), 1, 2, 3, and 5 days to determine the concentration change of the algal solution. The result shows that the addition of the composite photocatalytic film has obvious inhibition effect on the growth of the chromococcus micrantha compared with the algae without the composite photocatalytic film.
Example 3
The embodiment of the application provides a method for inhibiting harmful algae growth by using a composite photocatalytic film, which comprises the following steps:
1. preparation of g-C3N4[ PDI powder:
5g of melamine is placed in an alumina crucible, heated to 425 ℃ at a heating rate of 5 ℃/min, and then kept at the temperature for heating for 9 hours, thus preparing the precursor Melem. The Melem powder was suspended in ultrapure water at 100 ℃ for 3h, then filtered with the aid of a vacuum filter and the solid obtained was dried in an oven. The dried Melem powder was mixed homogeneously with PMDA in the same mass ratio. Putting the mixed mixture into a porcelain crucible with a cover, covering the porcelain crucible with the cover, putting the porcelain crucible into a muffle furnace again, heating to 325 ℃ at a heating rate of 6 ℃/min, calcining at 325 ℃ for 4h, and obtaining g-C3N4A/PDI powder.
2. G to C3N4Mixing PDI powder, an organic cross-linking agent and an organic solvent by an ultrasonic method, pouring the mixture on a substrate, and then air-drying to form a film:
weighing 1g of Cellulose Acetate (CA) powder, 0.5g of g-C prepared above3N4A/PDI powder. 15mL of dimethylformamide was measured in a 50mL beaker and the CA powder was added slowly while gently shaking to accelerate dissolution. After the CA is dissolved in a large amount, g-C is slowly added3N4/PDI powder with simultaneous shakingShaking up. And (4) performing ultrasonic treatment for 2h, adding 2mL of hot ultrapure water, and continuing ultrasonic treatment for 2 h. And (3) transferring 2.4mL of liquid into a 6cm smooth stainless steel sheet by using a liquid transfer gun while the sheet is hot, shaking to uniformly disperse the liquid, and air-drying the sheet in a fume hood for 2 hours to obtain the composite photocatalytic film.
3. The obtained composite photocatalytic film floats in a water solution containing harmful microalgae, and a simulated natural light source is turned on to realize growth inhibition on the harmful microalgae:
karenia mikimotoi (Karenia mikimotoi) is selected as an alga species of the target alga inhibiting. Selecting the concentration of 4X 104cells/mL, 35mL of the algal solution was put in a 100mL beaker. Taking two parts of the same algae liquid, putting one part of the algae liquid into the prepared composite photocatalytic film, and putting the other part of the algae liquid into the prepared composite photocatalytic film as light contrast without the composite photocatalytic film. Culturing the two algae solutions in a light incubator at 23 + -2 deg.C for 12h with a light-dark ratio of 12h to 12h and a light intensity of 2000Lux for 5 days. Samples were counted under microscope observation at 0, 0.5 (dark control), 1, 2, 3, 4, 5 days and the change in algal density was recorded. The result shows that the added composite photocatalytic film has obvious inhibition effect on the growth of algae. The composite photocatalytic film is removed, and the algae can not grow continuously. The result shows that the composite photocatalytic film can obviously inhibit the growth of the Karenia mikimotoi, can be recycled, and has no secondary pollution.
Comparative example
Comparative examples of the present application provide g-C alone3N4A method for testing the inhibitory effect of a membrane on harmful algae, the method comprising:
reference is made to the process of example 1, with the difference that no PMDA is added and the remaining steps correspond to those of example 1, i.e. only g-C are added3N4Cross-linking reaction with cellulose acetate and acetone to obtain g-C without PDI modification3N4Films (labeled g-C3N4 films), g-C alone was determined as in example 33N4The membrane has inhibiting effect on Microcystis aeruginosa, i.e. the g-C3N4The membrane floats on the microcystis aeruginosa solution to carry out the growth inhibition reaction, and the result is shown in figure 3. The results show that g-C of this comparative example3N4The membrane has no inhibiting effect on microalgae, and the microcystis aeruginosa grows normally.
The foregoing is only a preferred embodiment of the present application and it should be noted that those skilled in the art can make several improvements and modifications without departing from the principle of the present application, and these improvements and modifications should also be considered as the protection scope of the present application.
Claims (10)
1. A preparation method of a composite photocatalytic film for inhibiting the growth of harmful microalgae is characterized by comprising
Step 1, mixing melem and pyromellitic anhydride, and calcining to prepare pyromellitic anhydride modified graphite-phase carbon nitride powder;
step 2, crosslinking and mixing pyromellitic anhydride modified graphite-phase carbon nitride powder, a crosslinking agent and an organic solvent to prepare a crosslinked substance;
and 3, coating or soaking the cross-linked substance on a substrate, and drying until the film of the substrate falls off to obtain the composite photocatalytic film for inhibiting the growth of harmful microalgae.
2. The method according to claim 1, wherein the mass ratio of the melem to the pyromellitic anhydride in step 1 is (0.5 to 2.0): 1.
3. The preparation method according to claim 1, wherein in the step 1, the calcination temperature is 300-330 ℃, the calcination heating rate is 6-7 ℃/min, and the calcination time is 3-4 h.
4. The method according to claim 1, wherein in step 2, the crosslinking agent is selected from cellulose acetate and/or polystyrene; the organic solvent is selected from acetone or/and dimethylformamide.
5. The method according to claim 1, wherein in step 2, the ratio of crosslinking of the pyromellitic anhydride-modified graphite-phase carbon nitride powder, the crosslinking agent, and the organic solvent is (0.5 to 1.1) g: 1 g: 15 mL.
6. The method according to claim 1, wherein in step 3, the substrate is selected from a glass sheet, a stainless steel sheet, or a silicon wafer.
7. A composite photocatalytic film for inhibiting the growth of harmful microalgae, which is characterized by comprising the composite photocatalytic film prepared by the preparation method of any one of claims 1 to 6; the composite photocatalytic film can stably float on the water surface.
8. The use of the composite photocatalytic film prepared by the preparation method of any one of claims 1 to 6 for inhibiting the growth of harmful microalgae.
9. The use according to claim 8, comprising: the composite photocatalytic film prepared by the preparation method of any one of claims 1 to 6 is floated on a water surface containing harmful microalgae, and the growth of the harmful microalgae is inhibited under natural illumination.
10. The use of claim 9, wherein the harmful microalgae has a density of 5 x 104～11×106cells/mL; the harmful microalgae are selected from one or more of microcystis aeruginosa, Karenia mikimotoi and Chroococcum micranthum.
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