CN111994992A - Method for killing red tide algae by using supported composite photocatalyst - Google Patents
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Abstract
The invention belongs to the technical field of sterilization, and discloses a method for killing red tide algae by using a supported composite photocatalyst. Adding an organic solvent, a surfactant and ultrapure water into graphite-phase carbon nitride/nano titanium dioxide composite photocatalyst powder for ultrasonic treatment, coating the mixture on a substrate, and heating to 200-350 ℃ for calcination; placing the obtained load type graphite-phase carbon nitride/nano titanium dioxide composite photocatalyst in red tide algae suspension, turning on a visible light source, and adjusting the illumination intensity to be 5-30 mW/cm2The red tide algae suspension is made to flow homogeneously, and the light source is made to irradiate the surface of the composite photocatalyst to kill red tide algae. The composite photocatalyst has controllable load capacity, high photocatalytic efficiency and good stability, and the methodSimple, low cost, cyclic utilization and no secondary pollution, and can be popularized and applied in the field of red tide treatment.
Description
Technical Field
The invention belongs to the technical field of red tide treatment and photocatalytic environment-friendly nano materials, and particularly relates to a method for killing red tide algae by using a supported composite photocatalyst.
Background
In recent years, red tide frequently explodes in offshore areas of China, the occurrence area is enlarged, the duration is prolonged, and the damage day is more serious, so that China is apparently a country with more severe red tide disasters. Red tide, now known as the algal bloom of harmful algae (harmful algae, HABs) internationally, is a disastrous marine ecological abnormality phenomenon that some plankton or bacteria in seawater explosively proliferate or highly gather in a short time under certain environmental conditions to cause water discoloration and influence and harm the normal survival of other marine organisms. How to reduce or avoid other environmental problems brought by red tide in the process of treating red tide and meeting the requirements of protecting marine environment and sustainable development thereof are targets of effective red tide prevention and control in China. People begin research on red tide treatment as early as 19 th century, and common treatment methods can be divided into three major types, namely physical methods, chemical methods and biological methods. However, the physical method is neither economical nor convenient when treating red tide; the chemical method has no selectivity in the killing process, and can bring secondary pollution to water bodies; biological methods destroy biodiversity and may introduce new contamination. Therefore, how to find a proper treatment method and kill the marine red tide algae in a reasonable treatment way is a difficult problem to be overcome urgently.
The photocatalysis technology is a physical and chemical technology established based on a special energy band structure of a semiconductor, and the core of the photocatalysis technology is a semiconductor photocatalyst. The photocatalysis nano material is the semiconductor nano material which has photocatalysis activity and can kill algae and bacteria or degrade various chemical substances under the irradiation of ultraviolet light and even visible light, and the application of the current nano technology is the most extensive. After the photocatalyst nano material is irradiated by ultraviolet rays or visible light with certain energy, nano particles of the photocatalyst nano material are excited to generate electron-hole pairs with high activity, and then oxygen and water on the surface of the nano material undergo an oxidation-reduction reaction to finally generate superoxide anions and hydroxyl radicals with strong oxidizing property, so that the generated active species are utilized to kill algae, sterilize and degrade various pollutants and the like.
The nano titanium dioxide has the characteristics of large specific surface area, regular appearance and higher catalytic activity, has the advantages of low cost, no toxicity, long-term stability and the like, and is a photocatalytic nano material which is most widely applied in recent years. However, the larger band gap energy is 3.2eV, and the practical application of the nanoparticle is hindered by the high recombination rate of the electron-hole pairs formed by excitation. Therefore, how to extend the light absorption of titanium dioxide to the visible region and reduce the recombination of photo-generated charges is an urgent problem to be solved. The non-metal photocatalyst graphite-phase carbon nitride has a unique layered structure, excellent chemical stability and proper band gap energy, and the band gap energy of the non-metal photocatalyst graphite-phase carbon nitride is 2.7-2.8 eV along with the change of the thermal condensation degree. The delocalized conjugated p-structure of graphite-phase carbon nitride also provides relatively slow charge recombination and fast photo-induced charge separation during electron transfer, and thus, coupling of graphite-phase carbon nitride with titanium dioxide can enhance photocatalytic activity, with synergistic effects including enhanced photo-trapping, improved photo-stability, and efficient photo-excited charge separation, establishing a tight interface connection between the two semiconductors with appropriate conduction and valence band energy levels, and spatially smooth charge transfer through the heterojunction. Therefore, the graphite-phase carbon nitride with a wider band gap and the nano titanium dioxide are compounded to form a heterojunction, the problem that the nano carbon dioxide only responds to ultraviolet light can be solved, and meanwhile, the photo-generated electron-hole recombination rate is reduced due to the formation of the heterojunction, so that the photocatalytic quantum efficiency and the algae killing efficiency can be greatly improved. Research shows that the layered bulk graphite phase carbon nitride material is stripped to form a nanosheet, so that the photoproduction electron-hole separation rate can be further improved. Therefore, the development of materials for preparing composite catalysts which can realize wide spectral response and high electron-hole separation rate by loading nano titanium dioxide on graphite-phase carbon nitride nanosheets has been developed. In this respect, the nano titanium dioxide can be used as an intercalation material to assist the liquid phase stripping of the graphite phase carbon nitride, and the local high temperature and high pressure formed by the ultrasonic cavitation effect can enable the nano titanium dioxide to be simultaneously combined and loaded on the carbon nitride nanosheet by chemical bonds to form the graphite phase carbon nitride/nano titanium dioxide composite photocatalyst. In addition, the graphite phase carbon nitride/nano titanium dioxide composite photocatalyst is loaded on a proper substrate, so that the problem that the powder catalyst is not easy to recycle is solved, and the graphite phase carbon nitride/nano titanium dioxide composite photocatalyst has the advantages of low economic cost, simplicity in operation, no secondary pollution, high catalytic efficiency and the like. Until now, no relevant research and report on the use of a supported composite photocatalyst in killing red tide microalgae is found.
Disclosure of Invention
The invention provides a method for killing red tide algae by using a supported composite photocatalyst, aiming at the problem of treating marine red tide disasters caused by the red tide algae. The method utilizes sunlight to efficiently kill red tide algae, and the graphite phase carbon nitride/nano titanium dioxide composite photocatalyst is loaded on a proper substrate, so that the method has high photocatalytic efficiency and good recycling property, and avoids secondary pollution to the marine environment.
The above purpose of the invention is realized by the following technical scheme:
a method for killing red tide algae by using a supported composite photocatalyst comprises the following specific steps:
s1, mixing graphite-phase carbon nitride, nano titanium dioxide and an organic solvent A, performing ultrasonic treatment to obtain a suspension, drying to obtain graphite-phase carbon nitride/nano titanium dioxide composite photocatalyst powder, adding an organic solvent B, a surfactant and ultrapure water into the powder, performing ultrasonic treatment, coating the mixture on a substrate, heating to 200-350 ℃, and calcining to obtain a supported graphite-phase carbon nitride/nano titanium dioxide composite photocatalyst;
s2, placing the supported graphite-phase carbon nitride/nano titanium dioxide composite photocatalyst into the red tide algae suspension, turning on a visible light source, and adjusting the illumination intensity to be 5-30 mW/cm2The red tide algae suspension is in a uniform flowing state, and the light source is directed at one side of the loaded graphite phase carbon nitride/nano titanium dioxide composite photocatalyst for illumination, so that the red tide algae is killed.
Preferably, in the step S1, the mass ratio of the graphite-phase carbon nitride to the nano titanium dioxide is (1-9): (1-4): the loading amount of the graphite phase carbon nitride is 20-90 wt% of the graphite phase carbon nitride/nano titanium dioxide composite photocatalyst.
Preferably, in step S1, the usage ratio of the graphite-phase carbon nitride/nano titanium dioxide composite photocatalyst powder, the organic solvent B, the surfactant and the ultrapure water is (20-150) mg: (5-50) μ L: (2-10) μ L: (50-150) mu L.
Preferably, the organic solvent B in step S1 is acetic acid, formic acid, acetonitrile or trifluoroacetic acid; the surfactant is polyoxyethylene-8-octyl phenyl ether poly or vinyl pyrrolidone.
Preferably, the substrate in step S1 is a glass sheet, a titanium sheet, a polyethylene sheet, or a nickel foam.
Preferably, the organic solvent a in step S1 is ethanol, acetic acid, formic acid, acetonitrile or trifluoroacetic acid.
Preferably, the temperature rising rate in the step S1 is 2-8 ℃/min, and the calcination time is 0.5-1.5 h.
Preferably, the cell density in the red tide algae suspension in the step S2 is 5.0 × 103～3.5×104cells/mL。
Preferably, the visible light source in step S2 is a xenon lamp light source, an LED light source or natural sunlight.
Preferably, the illumination time in the step S2 is 0.5-1.5 h.
Preferably, the red tide algae in step S2 is keletonema mikimchii, skeletonema costatum or heterosigma akashiwo.
Compared with the prior art, the invention has the following beneficial effects:
1. the supported composite photocatalyst is formed by combining graphite phase carbon nitride and nano titanium dioxide, wherein bulk phase carbon nitride is peeled into carbon nitride nanosheets under the auxiliary action of the nano titanium dioxide in the ultrasonic process, and meanwhile, the nano titanium dioxide is supported on the carbon nitride nanosheets in the ultrasonic process, so that heterojunction is formed between the graphite phase carbon nitride and the nano titanium dioxide, thereby realizing efficient electron hole separation, reducing band gap energy, increasing light absorption in a visible light region and improving photocatalytic activity.
2. The method of the invention is simple, has low cost, has the characteristics of recyclability and no secondary pollution, and realizes the efficient killing of red tide algae under visible light.
3. The load capacity of the load type graphite phase carbon nitride/nano titanium dioxide composite photocatalyst is controllable, the photocatalytic efficiency is high, the stability is good, the problem that the powder photocatalyst is not easy to recover and causes secondary pollution when used for treating red tide is solved, and the load type graphite phase carbon nitride/nano titanium dioxide composite photocatalyst can be popularized and applied to treating red tide algae.
Drawings
FIG. 1 is a graph comparing the algae removal efficiency of the supported graphite-phase carbon nitride/nano titanium dioxide composite photocatalyst with the photo-control and dark-control groups, in an amount of 50 wt% in example 1;
fig. 2 is a microscopic comparison graph of algal cell morphology before and after algae killing by the supported graphite-phase carbon nitride/nano titanium dioxide composite photocatalyst of example 1.
Detailed Description
The invention is further described in the following description with reference to the figures and specific examples, which should not be construed as limiting the invention. It is within the scope of the present invention to make simple modifications or alterations to the methods, procedures or conditions of the present invention without departing from the spirit and substance of the invention; unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.
Example 1
1. Mixing 1.5g of bulk graphite phase carbon nitride and 1.5g of nano titanium dioxide with ethanol, stirring at room temperature, carrying out ultrasonic treatment to peel off the graphite phase carbon nitride and load the titanium dioxide in situ, drying and grinding the obtained suspension to obtain graphite phase carbon nitride/nano titanium dioxide composite photocatalyst powder;
2. weighing 50mg of the prepared graphite-phase carbon nitride/nano titanium dioxide composite photocatalyst powder, adding 15 mu L of acetic acid, 5 mu L of polyoxyethylene-8-octyl phenyl ether (triton TX-100) and 100 mu L of ultrapure water, carrying out ultrasonic treatment, and coating the glass sheet with the powder; placing the glass sheet loaded with the graphite phase carbon nitride/nano titanium dioxide composite photocatalyst powder in a crucible, heating to 300 ℃ at a speed of 5 ℃/min in a muffle furnace, calcining for 1h, and cooling to obtain the loaded graphite phase carbon nitride/nano titanium dioxide composite photocatalyst.
3. Selecting red tide microalgae Karenia mikimotoi (Karenia mikimotoi) as target inactivated algae species. The Karenia mikimotoi is inoculated into an f/2 seawater culture medium in a sterile room, the specification of a culture bottle is 500mL, the Karenia mikimotoi is placed in an illumination incubator for culture, the temperature of the illumination incubator is (23 +/-2 ℃), the light-dark ratio is 12h:12h, the illumination intensity is 2000Lux, and the culture is continuously carried out until the logarithmic growth phase of the Karenia mikimotoi. Selecting Karenia mikimotoi in logarithmic growth phase as an inactivated strain, measuring 100mL of Karenia mikimotoi suspension and pouring the Karenia mikimotoi suspension into a glass vessel when the cell density is about 35000 cells/mL.
4. Placing the prepared graphite phase carbon nitride/nano titanium dioxide composite photocatalyst with the graphite phase carbon nitride loading of 50 wt% into a glass ware filled with 100mL of red tide algae liquid, turning on a xenon lamp light source (provided with a band-pass visible light filter with lambda being 420 nm), and adjusting the illumination intensity to 15.0mW/cm by using a light intensity meter2The Karenia mikimotoi suspension is in a uniform flowing state by using a stirrer, the Karenia mikimotoi is prevented from depositing at the bottom of a reactor in the reaction process, the photocatalytic algae killing effect is weakened, then a light source is aligned to one surface of the loaded graphite phase carbon nitride/nano titanium dioxide composite photocatalyst, the photocatalytic reaction is started immediately, the illumination reaction time is 1h, and the red tide algae are killed. Immediately turning off the light source and taking out the catalyst after the photoreaction is finished, then giving a dark room environment to the reacted Kerenia mikimotoi suspension, carrying out dark reaction for 1h, and taking a proper amount of algae liquid every 10min at intervals during 2h of the dark and bright reaction to measure the concentration value of chlorophyll a.
FIG. 1 is a graph comparing the algae removal efficiency of the graphite phase carbon nitride/nano titanium dioxide composite photocatalyst with the graphite phase carbon nitride loading of 50 wt% in example 1 with that of a control group. As shown in fig. 1, the concentration of chlorophyll-a rapidly decreased in the initial 10 minutes of the photocatalytic reaction, while the concentration of chlorophyll-a was still gradually decreased in the subsequent photocatalytic process; after the algae liquid after the photocatalytic reaction is placed in a dark environment for 1 hour, the concentration of chlorophyll a of the algae liquid of a light control group without a catalyst is observed to rapidly rise to an initial value, the concentration of the chlorophyll a of the algae liquid of an experiment group with the catalyst of 50 wt% does not rise, the concentration is kept unchanged, and the concentration value of the chlorophyll a is not restored to the initial value, which indicates that Karenia mikimotoi is damaged in the photocatalytic process, and the light reaction center collapses and loses the capability of recovering chlorophyll fluorescence. The concentration of chlorophyll a in the Karenia mikimotoi in the photocatalysis process is measured by a chlorophyll fluorescence meter, and the concentration value of the chlorophyll a is measured by the chlorophyll fluorescence value of the chlorophyll fluorescence meter, so that the chlorophyll fluorescence value of the algae is rapidly reduced after the photoreaction center of the algae is closed after the illumination intensity exceeding the illumination intensity required by the photosynthesis of the algae is given, the measured concentration of the chlorophyll a is also rapidly reduced, if the algae is not damaged in the illumination process of the intensity, the photoreaction center of the algae which is not damaged in the illumination process is opened again after the illumination is finished and the chlorophyll fluorescence value is gradually recovered to the initial value after the photoreaction center of the algae which is not damaged in the illumination process is given a dark environment again after the illumination is finished.
Fig. 2 is a microscopic comparison graph of algal cell morphology before and after algae killing by the supported graphite-phase carbon nitride/nano titanium dioxide composite photocatalyst of example 1. Wherein, (a) is a complete cell morphology diagram of Karenia mikimotoi before photocatalytic algae killing, and (b) is a ruptured cell morphology diagram of Karenia mikimotoi after photocatalytic algae killing. As shown in fig. 2, the complete deformation and rupture of the karenia mikimotoi cells after the photocatalytic reaction are observed through the cell states of the karenia mikimotoi before and after the photocatalytic reaction photographed under a microscope, which proves that the cells are damaged and ruptured in the photocatalytic process, and the cells are dead. The result shows that the supported graphite phase carbon nitride/nano titanium dioxide composite photocatalyst can effectively kill red tide algae, has high photocatalytic activity, is easy to recycle and does not produce secondary pollution.
Example 2
1. Mixing 0.5g of bulk graphite phase carbon nitride and 2.0g of nano titanium dioxide with ethanol, stirring at room temperature, carrying out ultrasonic treatment to peel off the graphite phase carbon nitride and load the titanium dioxide in situ, drying and grinding the obtained suspension to obtain graphite phase carbon nitride/nano titanium dioxide composite photocatalyst powder;
2. weighing 50mg of the prepared graphite-phase carbon nitride/nano titanium dioxide composite photocatalyst powder, adding 15 mu L of acetic acid, 5 mu L of triton (TX-100) and 100 mu L of ultrapure water, carrying out ultrasonic treatment, and coating the obtained product on a titanium sheet; placing a titanium sheet loaded with the graphite phase carbon nitride/nano titanium dioxide composite photocatalyst powder in a crucible, heating to 200 ℃ at a speed of 2 ℃/min in a muffle furnace, calcining for 0.5h, and cooling to obtain the loaded graphite phase carbon nitride/nano titanium dioxide composite photocatalyst.
3. Skeletonema costatum in red tide algae is selected as a target inactivated algae species. The skeletonema costatum is put into a seawater culture medium in a sterile room, the specification of a culture bottle is 500mL, the skeletonema costatum is placed into a light incubator for culture, the temperature of the light incubator is 25 +/-2 ℃, and the culture is continued until the logarithmic growth phase of the skeletonema costatum. Selecting skeletonema costatum in logarithmic growth phase as an inactivated algae seed, measuring 50mL skeletonema costatum suspension and pouring the skeletonema costatum suspension into a glass ware when the cell density is about 5000 cells/mL.
4. Placing a piece of prepared graphite phase carbon nitride/nano titanium dioxide composite photocatalyst with the graphite phase carbon nitride loading capacity of 20 wt% in a glassware filled with 50mL of red tide algae solution. The xenon lamp light source (equipped with a band-pass visible light filter with lambda of 420 nm) was turned on, and the light intensity was adjusted to 30.0mW/cm using a light intensity meter2The skeletonema costatum suspension is in a uniform flowing state by using the stirrer, so that the skeletonema costatum is prevented from settling at the bottom of the reactor in the reaction process, and the photocatalytic algae killing effect is weakened. Then, a light source is aligned to one surface of the loaded graphite phase carbon nitride/nano titanium dioxide composite photocatalyst, photocatalytic reaction is started immediately, the illumination reaction time is 1h, and the red tide algae are killed. Immediately turning off the light source and taking out the catalyst after the photoreaction is finished, then giving a darkroom environment to the reacted skeletonema costatum suspension, carrying out dark reaction for 1h, and taking a proper amount of algae liquid every 10min at intervals during 2h of the dark and bright reaction to measure the concentration value of chlorophyll a of the skeletonema costatum suspension. Experimental results show that the supported graphite-phase carbon nitride/nano titanium dioxide composite photocatalyst can effectively kill red tide algae, has high photocatalytic activity, is easy to recycle and does not produce secondary pollution.
Example 3
1. Mixing 4.5g of bulk graphite phase carbon nitride and 0.5g of nano titanium dioxide with ethanol, stirring at room temperature, carrying out ultrasonic treatment to peel off the graphite phase carbon nitride and load the titanium dioxide in situ, drying and grinding the obtained suspension to obtain graphite phase carbon nitride/nano titanium dioxide composite photocatalyst powder;
2. weighing 50mg of the prepared graphite-phase carbon nitride/nano titanium dioxide composite photocatalyst powder, adding 15 mu L of acetic acid, 5 mu L of triton (TX-100) and 100 mu L of ultrapure water, carrying out ultrasonic treatment, and coating the powder on foamed nickel; placing the foam nickel loaded with the graphite phase carbon nitride/nano titanium dioxide composite photocatalyst powder into a crucible, heating to 200 ℃ at a rate of 2 ℃/min in a muffle furnace, calcining for 0.5h, and cooling to obtain the loaded graphite phase carbon nitride/nano titanium dioxide composite photocatalyst.
3. The red tide algae, red tide heterosigma gulfweed (Heterosigmaakashiwo), was selected as the target inactivated algal species. The red tide heterosigma akashiwo alga is inoculated into a seawater culture medium in a sterile room, the specification of a culture bottle is 500mL, and the culture bottle is placed in an illumination incubator for culture, the temperature of the illumination incubator is 25 +/-2 ℃, and the culture is continuously carried out until the logarithmic growth phase of the red tide heterosigma akashiwo alga. Selecting red tide heterosigma akashiwo alga in logarithmic growth phase as an inactivated alga strain, measuring 150mL of red tide heterosigma akashiwo alga suspension when the cell density is about 15000cells/mL, and pouring the red tide heterosigma akashiwo alga suspension into a glass vessel.
4. Placing a piece of prepared graphite phase carbon nitride/nano titanium dioxide composite photocatalyst with the graphite phase carbon nitride loading capacity of 90 wt% in a glass ware filled with 150mL of red tide algae solution. The xenon lamp light source (equipped with a band-pass visible light filter with lambda of 420 nm) was turned on, and the light intensity was adjusted to 5.0mW/cm using a light intensity meter2The suspension of the red tide heterosigma akashiwo alga is in a uniform flowing state by using the stirrer, so that the red tide heterosigma akashiwo alga is prevented from being deposited at the bottom of the reactor in the reaction process, and the photocatalysis algae killing effect is weakened. Then, a light source is aligned to one surface of the loaded graphite phase carbon nitride/nano titanium dioxide composite photocatalyst, photocatalytic reaction is started immediately, the illumination reaction time is 1h, and the red tide algae are killed. Immediately turning off the light source and taking out the catalyst after the light reactionThe preparation is then added into the reacted red tide gulfweed suspension for dark reaction for 1h, and appropriate amount of algae liquid is taken at intervals of 10min by a chlorophyll fluorescence instrument during 2h of the dark reaction to determine the concentration value of chlorophyll a. Experimental results show that the supported graphite-phase carbon nitride/nano titanium dioxide composite photocatalyst can effectively kill red tide algae, has high photocatalytic activity, is easy to recycle and does not produce secondary pollution.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for killing red tide algae by using a supported composite photocatalyst is characterized by comprising the following specific steps:
s1, mixing graphite-phase carbon nitride, nano titanium dioxide and an organic solvent A, performing ultrasonic treatment to obtain a suspension, drying to obtain graphite-phase carbon nitride/nano titanium dioxide composite photocatalyst powder, adding an organic solvent B, a surfactant and ultrapure water into the powder, performing ultrasonic treatment, coating the mixture on a substrate, heating to 200-350 ℃, and calcining to obtain a supported graphite-phase carbon nitride/nano titanium dioxide composite photocatalyst;
s2, placing the supported graphite-phase carbon nitride/nano titanium dioxide composite photocatalyst into the red tide algae suspension, turning on a visible light source, and adjusting the illumination intensity to be 5-30 mW/cm2The red tide algae suspension is in a uniform flowing state, and the light source is directed at one side of the loaded graphite phase carbon nitride/nano titanium dioxide composite photocatalyst for illumination, so that the red tide algae is killed.
2. The method for killing red tide algae by using the supported composite photocatalyst as claimed in claim 1, wherein the mass ratio of the graphite-phase carbon nitride to the nano titanium dioxide in step S1 is (1-9): (1-4): the loading amount of the graphite phase carbon nitride is 20-90 wt% of the graphite phase carbon nitride/nano titanium dioxide composite photocatalyst.
3. The method for killing red tide algae by using the supported composite photocatalyst as claimed in claim 1, wherein the usage ratio of the graphite-phase carbon nitride/nano titanium dioxide composite photocatalyst powder, the organic solvent B, the surfactant and the ultrapure water in step S1 is (20-150) mg: (5-50) μ L: (2-10) μ L: (50-150) mu L; the organic solvent B is acetic acid, formic acid, acetonitrile or trifluoroacetic acid; the surfactant is polyoxyethylene-8-octyl phenyl ether poly or vinyl pyrrolidone.
4. The method for killing red tide algae by using the supported composite photocatalyst as claimed in claim 1, wherein the substrate in step S1 is a glass sheet, a titanium sheet, a polyethylene sheet or a nickel foam.
5. The method for killing red tide algae by using the supported composite photocatalyst as claimed in claim 1, wherein the organic solvent A in step S1 is ethanol, acetic acid, formic acid, acetonitrile or trifluoroacetic acid.
6. The method for killing red tide algae by using the supported composite photocatalyst as claimed in claim 1, wherein the temperature rise rate in step S1 is 2-8 ℃/min, and the calcination time is 0.5-1.5 h.
7. The method for killing red tide algae by using the supported composite photocatalyst as claimed in claim 1, wherein the cell density in the red tide algae suspension in step S2 is 5.0 x 103～3.5×104cells/mL。
8. The method for killing red tide algae by using the supported composite photocatalyst as claimed in claim 1, wherein the visible light source in step S2 is a xenon lamp light source, an LED light source or natural sunlight.
9. The method for killing red tide algae by using the supported composite photocatalyst as claimed in claim 1, wherein the illumination time in step S2 is 0.5-1.5 h.
10. The method for killing red tide algae by using the supported composite photocatalyst as claimed in claim 1, wherein the red tide algae in step S2 is keletonema mikimchii, skeletonema costatum or heterosigma akashiwo.
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| CN113856757A (en) * | 2021-11-04 | 2021-12-31 | 广东工业大学 | Polydopamine-modified carbon nitride/titanium dioxide-loaded foam nickel composite photocatalyst and preparation method and application thereof |
| CN115254168A (en) * | 2022-08-10 | 2022-11-01 | 江西省生态环境科学研究与规划院 | Composite photocatalytic material and preparation method and application thereof |
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| CN115254168B (en) * | 2022-08-10 | 2023-09-12 | 江西省生态环境科学研究与规划院 | Composite photocatalytic material and preparation method and application thereof |
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