Nickel-containing carbon nitride loaded chalcopyrite composite material and application thereof in photocatalytic algae removal

Abstract

This invention belongs to the field of photocatalytic algae removal technology, specifically relating to a nickel-containing carbon nitride-supported chalcopyrite composite material and its photocatalytic algae removal application. The invention first prepares g-C3N4 by high-temperature polymerization of a nitrogen-containing carbon-based precursor, then modifies it with nickel chloride to obtain Ni-g-C3N4. Subsequently, this is added to a precursor solution containing iron salts, copper salts, and thiourea. After hydrothermal reaction, the resulting product is calcined to obtain the nickel-containing carbon nitride-supported chalcopyrite composite material CuFeS2-Ni-g-C3N4. The nickel-containing graphitic carbon nitride-natural chalcopyrite in-situ coupled material synthesized in this invention is a photocatalytic material that combines highly efficient inactivation of Microcystis aeruginosa and degradation of algal toxins. It can directly utilize visible light such as sunlight to inactivate Microcystis aeruginosa and rapidly degrade algal toxins in flowing water, making it an environmentally friendly sterilization material with significant practical value.

Description

Technical Field

[0001] This invention belongs to the field of photocatalytic algae removal technology, specifically relating to a nickel-containing carbon nitride-supported chalcopyrite composite material and its photocatalytic algae removal application. Background Technology

[0002] Microcystis aeruginosa, belonging to the genus Microcystis in the phylum Cyanobacteria, is a representative harmful algae species most prone to causing algal blooms in freshwater bodies worldwide. Its outbreaks are not driven by a single factor, but rather by the synergistic effects of multiple factors, including eutrophication, climate change, altered hydrological conditions, and interbiotic interactions. In recent years, with increased human activity and the intensification of global warming, the range, frequency, and duration of Microcystis aeruginosa blooms have continued to expand, gradually extending from traditional large lakes to small and medium-sized reservoirs, urban landscape water bodies, aquaculture ponds, and river tributaries. This phenomenon not only disrupts the structural and functional integrity of aquatic ecosystems but also poses a serious threat to drinking water safety, human health, and socio-economic development, becoming a major ecological and environmental challenge urgently needing to be addressed in the field of water environment.

[0003] Photocatalytic oxidation technology, as an important branch of advanced oxidation technology, has shown broad application prospects in the field of water pollutant treatment due to its advantages such as mild reaction conditions, no secondary pollution, and strong oxidation capacity, especially suitable for the killing and control of Microcystis aeruginosa. The core of this technology is the photocatalyst, whose performance directly determines the photocatalytic algae removal effect. Graphite-phase carbon nitride (g-C3N4), as a novel metal-free semiconductor photocatalyst, has advantages such as simple preparation, low cost, good chemical stability, and strong visible light responsiveness, and has attracted widespread attention in the fields of photocatalytic degradation of pollutants, sterilization, and algae removal. However, pure g-C3N4 has inherent defects such as a fast photogenerated electron-hole recombination rate, small specific surface area, and limited light absorption range, which significantly limit its photocatalytic activity and make it difficult to meet the actual needs of algae removal in water bodies. Therefore, modification of g-C3N4 has become a key research direction. Metal sulfides, with their unique electronic structure and narrow band gap characteristics, have become one of the ideal materials for modifying g-C3N4. CuFeS2, as a ternary sulfide semiconductor, possesses excellent visible light absorption, good conductivity, and catalytic activity. Rich in Fe, it can participate in Fenton-like reactions to generate a large number of reactive oxygen species, further enhancing photocatalytic oxidation performance and demonstrating promising application potential in the field of photocatalysis. Meanwhile, nickel (Ni) and its sulfides, as highly efficient co-catalysts, can effectively promote the separation and transfer of photogenerated electron-hole pairs, reduce the charge recombination rate, and provide abundant active sites, significantly improving the photocatalytic activity of the composite material. Therefore, it is an effective modifier for improving the photocatalytic performance of g-C3N4.

[0004] In summary, the development of a highly efficient method for inactivating Microcystis aeruginosa based on g-C3N4 and CuFeS2 has significant research value and practical application. Summary of the Invention

[0005] To overcome the shortcomings of the prior art, this invention provides a method for synthesizing CuFeS2-Ni-g-C3N4 composite material by in-situ coupling of nickel-containing graphitic carbon nitride with natural chalcopyrite. The synthesized CuFeS2-Ni-g-C3N4 material is a photocatalytic material that combines efficient inactivation of Microcystis aeruginosa and degradation of algal toxins. It can directly utilize sunlight to achieve the inactivation of Microcystis aeruginosa and rapid degradation of algal toxins in flowing water, greatly improving the photocatalytic sterilization efficiency.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: The first aspect of this invention provides a method for synthesizing a nickel-containing carbon nitride-supported chalcopyrite composite material (CuFeS2-Ni-g-C3N4), the method comprising the following steps: S1. Using a nitrogen-containing carbon-based precursor as raw material, a graphitic carbon nitride (g-C3N4) precursor was prepared by high-temperature polymerization. Subsequently, the graphitic carbon nitride (g-C3N4) was dispersed in water, ultrasonically treated, and dried to achieve its modification. Then, the modified graphitic carbon nitride (g-C3N4) was dispersed in a water-alcohol mixed solution, and a nickel chloride solution was added. After stirring in a water bath, washing, and drying, the loading modification was completed, and finally, a nickel carbon nitride (Ni / g-C3N4) composite material was obtained. S2. Using Ni / g-C3N4 composite material as a base, it is dispersed in water; then copper salt solution, iron salt solution and thiourea solution are added, and after heating and stirring, the resulting mixture is subjected to hydrothermal reaction. After the reaction, the precipitate is collected and washed; after washing, the precipitate is dried and calcined in an inert gas atmosphere to obtain nickel-containing carbon nitride supported chalcopyrite composite material (CuFeS2-Ni-g-C3N4).

[0007] The CuFeS2-Ni-g-C3N4 prepared using the method of this invention can be used as a composite photocatalyst for photocatalytic-Fenton in-situ coupling inactivation of Microcystis aeruginosa. This catalyst can generate hydrogen peroxide in situ under visible light irradiation, and its own ferrous ions can activate the generated hydrogen peroxide, thus constructing a highly efficient photo-Fenton in-situ coupling system. During the photocatalytic reaction, hydrogen peroxide reacts with ferrous ions to generate a large number of reactive oxygen species such as hydroxyl radicals and singlet oxygen. On the one hand, hydrogen peroxide can disrupt the permeability of the Microcystis aeruginosa cell membrane; on the other hand, the participation of ferrous ions significantly increases the production of hydroxyl radicals. The synergistic effect of these two factors greatly improves the photocatalytic inactivation efficiency of Microcystis aeruginosa. Furthermore, this catalyst can also be used to degrade algal toxins in the aquatic environment, demonstrating significant practical value.

[0008] Preferably, the nitrogen-containing carbon-based precursor in step S1 includes urea, melamine, dicyandiamide, or thiourea.

[0009] Preferably, the high-temperature polymerization in step S1 is carried out at a temperature of 450℃ to 650℃, a heating rate of 5℃ / min to 30℃ / min, and a time of 1 to 3 hours.

[0010] Preferably, the ultrasonic treatment in step S1 is ultrasonic treatment at a power of 40-60W for 15-30 minutes.

[0011] Preferably, the water-alcohol mixture in step S1 is a water-ethanol mixture, with a volume ratio of water to ethanol of 1:3-5.

[0012] Preferably, in step S1, the ratio of graphitic carbon nitride (g-C3N4) to nickel chloride solution is 45-55 mg: 7-15 mL, and the concentration of nickel chloride solution is 1.3-1.8 mg / mL.

[0013] Preferably, the water bath stirring temperature in step S1 is 60℃~80℃, the stirring speed is 7000~9000 rpm / min, and the stirring time is 3~6h.

[0014] Preferably, the temperature of the hydrothermal reaction in step S2 is 180℃~220℃, the heating rate is 5℃~10℃, and the reaction time is 12h~18h.

[0015] Preferably, the calcination temperature in step S2 is 300℃~600℃, the heating rate is 2℃ / min~15℃ / min, and the reaction time is 60min~180min.

[0016] Preferably, the iron salt in step S2 includes ferric chloride and ferric nitrate, and the copper salt includes copper nitrate and copper chloride.

[0017] Preferably, the molar ratio of copper salt, iron salt and thiourea in step S2 is 1:1.0-1.2:2.0-2.5.

[0018] Preferably, the mass ratio of the Ni / g-C3N4 composite material to the total amount of copper salt, iron salt and thiourea in step S2 is 1:0.2 to 2.0.

[0019] Preferably, the ratio of graphitic carbon nitride (g-C3N4) to nickel chloride solution is 45-55 mg: 7-15 mL, and the concentration of nickel chloride solution is 1.3-1.8 mg / mL.

[0020] The second aspect of the present invention also provides a nickel-containing carbon nitride-supported chalcopyrite composite material prepared by the preparation method described in the first aspect.

[0021] The third aspect of the present invention also provides the application of the nickel-containing carbon nitride-supported chalcopyrite composite material described in the second aspect in the inactivation of Microcystis aeruginosa in aquatic environments and / or the degradation of algal toxins in aquatic environments.

[0022] Preferably, the application is performed under visible light drive, wherein the visible light source is a xenon lamp source, an LED source, or a natural sunlight source.

[0023] Compared with the prior art, the beneficial effects of the present invention are: This invention discloses a method for synthesizing the composite material CuFeS2-Ni-g-C3N4 by in-situ coupling of nickel-containing graphitic carbon nitride and natural chalcopyrite. The method first involves high-temperature polymerization of a nitrogen-containing carbon-based precursor to obtain g-C3N4, followed by loading and modification with nickel chloride to obtain Ni-g-C3N4. This Ni-g-C3N4 is then added to a precursor solution containing iron salts, copper salts, and thiourea. After hydrothermal reaction, the resulting product is calcined to obtain the final product. The nickel-containing graphitic carbon nitride-natural chalcopyrite in-situ coupled material synthesized by this invention is a photocatalytic material that combines highly efficient inactivation of Microcystis aeruginosa and degradation of algal toxins. It can directly utilize visible light such as sunlight to inactivate Microcystis aeruginosa and rapidly degrade algal toxins in flowing water, making it an environmentally friendly sterilization material.

[0024] This composite material not only expands the visible light response range of the original graphitic carbon nitride, but also significantly improves the separation and transport efficiency of photogenerated carriers and the light absorption performance. At the same time, the in-situ coupling system can enhance the synergistic effect of active free radicals such as hydrogen peroxide and singlet oxygen, resulting in a stronger destructive effect on the cell membrane of Microcystis aeruginosa, thereby achieving efficient killing of Microcystis aeruginosa and rapid degradation of algal toxins, which has important practical value. Attached Figure Description

[0025] Figure 1TEM image of CuFeS2 / Ni-g-C3N4, an in-situ coupling material between nickel-containing graphitic carbon nitride and natural chalcopyrite; Figure 2 The results of the test on the killing performance of different photocatalytic materials CuFeS2 / Ni-g-C3N4, CuFeS2, g-C3N4 and Ni-g-C3N4 on Microcystis aeruginosa; Figure 3 The results show the degradation performance of different photocatalytic materials CuFeS2 / Ni-g-C3N4, CuFeS2, g-C3N4, and Ni-g-C3N4 on algal toxins. Detailed Implementation

[0026] The specific embodiments of the present invention will be further described below. It should be noted that these descriptions are for the purpose of aiding understanding the present invention, but do not constitute a limitation thereof. Furthermore, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0027] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods, and the experimental materials used in the following embodiments are all available through conventional commercial channels.

[0028] This invention provides a method for synthesizing nickel-containing carbon nitride-supported chalcopyrite. Using g-C3N4 as a carrier, CuFeS2 and Ni are loaded through a rational preparation process to construct a CuFeS2 / Ni-g-C3N4 composite photocatalytic material. The effects of the preparation conditions on the material's structure and photocatalytic performance are systematically studied. A series of characterization methods are used to clarify the microstructure, optical properties, and composition of the composite material. Simultaneously, using *Microcystis aeruginosa* as the target organism, the photocatalytic killing effect of the composite material is evaluated, and the effects of factors such as illumination time and material dosage on algae removal efficiency are explored, preliminarily revealing its photocatalytic algae removal mechanism.

[0029] To fully and clearly present the technical solution and significant advantages of the present invention, the present invention will be described in detail below with reference to specific embodiments.

[0030] Example 1: Preparation of CuFeS2 / Ni-g-C3N4, a nickel-containing carbon nitride-supported chalcopyrite composite material. (1) Weigh 10g of urea powder and place it in a porcelain crucible. Calcinate it in a muffle furnace (5 ℃ / min, 550 ℃, 2 h) to obtain a pale yellow solid, thus obtaining the precursor material g-C3N4. Disperse the obtained C3N4 powder in pure water, let it stand for 30 min, and then sonicate it at room temperature for 20 min. Collect the solid product and dry it overnight in a vacuum drying oven. Weigh 50mg of the dried g-C3N4 solid and add it to a mixed solution of 40mL water and 10mL anhydrous ethanol. Disperse it evenly by sonication. Then slowly add 10mL of nickel chloride solution with a concentration of 1.5 mg / mL. Stir in a water bath (70 ℃, 8000 rpm, 4 h) and sonicate for 20 min to mix thoroughly. Centrifuge to collect the product and wash it three times. Finally, place it in a vacuum oven and dry it at 80 ℃ for 12 h to obtain the target product Ni / g-C3N4.

[0031] (2) Using 1 g Ni / g-C3N4 composite material as a substrate, it was dispersed in 100 mL of water and sonicated for 1 h to ensure complete dispersion. Subsequently, 13.6 mL of 0.1 M copper nitrate solution, 13.6 mL of 0.1 M ferric chloride solution, and 10.9 mL of 0.25 M thiourea solution were added sequentially, and the mixture was stirred at 60 °C for 30 min. The resulting mixture was then subjected to a hydrothermal reaction (5 °C / min, 220 °C, 12 h). After the reaction, the supernatant was discarded, the precipitate was collected and washed three times; the washed precipitate was placed in a vacuum oven and dried at 80 °C for 12 h. Finally, the dried product was placed in a tube furnace and calcined at 350 °C (5 °C / min, 2 h) under a nitrogen atmosphere to obtain the target product CuFeS2 / Ni-g-C3N4.

[0032] Figure 1 The TEM images show that CuFeS was grown in situ on Ni / g-C3N4 sheets during the synthesis process, rather than being a simple physical mixture.

[0033] Example 2: Preparation of CuFeS2 / Ni-g-C3N4, a nickel-containing carbon nitride-supported chalcopyrite composite material. (1) A certain amount of urea powder was weighed and placed in a porcelain crucible. It was calcined in a muffle furnace (5 ℃ / min, 550 ℃, 2 h) to obtain a light yellow solid, which yielded the precursor material g-C3N4. The obtained g-C3N4 powder was dispersed in pure water and allowed to stand for 30 min. It was then sonicated at room temperature for 20 min. The solid product was collected and dried overnight in a vacuum drying oven. 50 mg of the dried g-C3N4 solid was weighed and added to a mixed solution of 40 mL water and 10 mL anhydrous ethanol. The mixture was sonicated and dispersed evenly. Then, 10 mL of nickel chloride solution with a concentration of 1.5 mg / mL was slowly added. The mixture was stirred in a water bath (70 ℃, 8000 rpm, 4 h) and sonicated for 20 min to mix thoroughly. The product was collected by centrifugation and washed three times. Finally, it was placed in a vacuum oven and dried at 80 ℃ for 12 h to obtain the target product Ni / g-C3N4.

[0034] (2) Using 1 g Ni / g-C3N4 composite material as a substrate, it was dispersed in 100 mL of water and sonicated for 1 h to ensure complete dispersion. Subsequently, 23.4 mL of 0.1 M copper nitrate solution, 25.7 mL of 0.1 M ferric chloride solution, and 20.6 mL of 0.25 M thiourea solution were added sequentially, and the mixture was stirred at 60 °C for 30 min. The resulting mixture was then subjected to a hydrothermal reaction (5 °C / min, 220 °C, 12 h). After the reaction, the supernatant was discarded, the precipitate was collected and washed three times; the washed precipitate was placed in a vacuum oven and dried at 80 °C for 12 h. Finally, the dried product was placed in a tube furnace and calcined at 350 °C (5 °C / min, 2 h) under a nitrogen atmosphere to obtain the target product CuFeS2 / Ni-g-C3N4.

[0035] Example 3: Preparation of CuFeS2 / Ni-g-C3N4, a nickel-containing carbon nitride-supported chalcopyrite composite material. (1) A certain amount of urea powder was weighed and placed in a porcelain crucible. It was calcined in a muffle furnace (5 ℃ / min, 550 ℃, 2 h) to obtain a light yellow solid, which yielded the precursor material g-C3N4. The obtained g-C3N4 powder was dispersed in pure water and allowed to stand for 30 min. It was then sonicated at room temperature for 20 min. The solid product was collected and dried overnight in a vacuum drying oven. 50 mg of the dried g-C3N4 solid was weighed and added to a mixed solution of 40 mL water and 10 mL anhydrous ethanol. The mixture was sonicated and dispersed evenly. Then, 10 mL of nickel chloride solution with a concentration of 1.5 mg / mL was slowly added. The mixture was stirred in a water bath (70 ℃, 8000 rpm, 4 h) and sonicated for 20 min to mix thoroughly. The product was collected by centrifugation and washed three times. Finally, it was placed in a vacuum oven and dried at 80 ℃ for 12 h to obtain the target product Ni / g-C3N4.

[0036] (2) Using 1 g Ni / g-C3N4 composite material as a substrate, it was dispersed in 100 mL of water and sonicated for 1 h to ensure complete dispersion. Subsequently, 6.1 mL of 0.1 M copper nitrate solution, 6.1 mL of 0.1 M ferric chloride solution, and 4.8 mL of 0.25 M thiourea solution were added sequentially, and the mixture was stirred at 60 °C for 30 min. The resulting mixture was then subjected to a hydrothermal reaction (5 °C / min, 220 °C, 12 h). After the reaction, the supernatant was discarded, the precipitate was collected and washed three times; the washed precipitate was placed in a vacuum oven and dried at 80 °C for 12 h. Finally, the dried product was placed in a tube furnace and calcined at 350 °C (5 °C / min, 2 h) under a nitrogen atmosphere to obtain the target product CuFeS2 / Ni-g-C3N4.

[0037] Comparative Example: Preparation of CuFeS2 Control 13.6 mL of 0.1 M copper nitrate solution, 13.6 mL of 0.1 M ferric chloride solution, and 10.9 mL of 0.25 M thiourea solution were added to 100 mL of water and stirred at 60 °C for 30 min. The resulting mixture was then subjected to a hydrothermal reaction (5 °C / min, 220 °C, 12 h). After the reaction, the supernatant was discarded, the precipitate was collected and washed three times. The washed precipitate was then placed in a vacuum oven and dried at 80 °C for 12 h. Finally, the dried product was placed in a tube furnace and calcined at 350 °C (5 °C / min, 2 h) under a nitrogen atmosphere to obtain the target product CuFeS2.

[0038] Experimental Example: Verification of the Killing Effect of CuFeS2 / Ni-g-C3N4 on Microcystis aeruginosa and its Degradation Effect on Algal Toxins (1) Test method 1) Dissolve 1.70 g of BG-11 culture medium powder in 1000 mL of ultrapure water, sterilize in an autoclave (121℃, 30 minutes), and cool to room temperature. When Microcystis aeruginosa FACHB-905 reaches the plateau phase, take an appropriate amount of algal solution, add an equal volume of BG11 culture medium, inoculate into a 500 mL Erlenmeyer flask, and incubate the algal solution in a light incubator. Take 40 mL of the solution at a density of approximately 1×10⁻⁶. 7 The experiment was conducted using an algal cell solution containing 10 mg of photocatalyst (CuFeS2-Nig-C3N4, CuFeS2, Ni / g-C3N4). The solution was then shaken and mixed to obtain a suspension. A control group without the catalyst was also included.

[0039] 2) Place the above suspension under a xenon lamp light source and turn on the light source (light intensity: 60mw / cm²).2 Photocatalytic performance was tested. During the Microcystis aeruginosa inactivation test, samples were taken every 1 hour to determine the algal concentration. Simultaneously, the algal solution was filtered using a 0.22 μm aqueous microporous membrane, and the concentration of microcystin toxin MC-LR was determined using an ultra-high performance liquid chromatography-quadrupole-electrostatic field orbital trap mass spectrometer equipped with a C18 column (100 mm × 2.1 mm, 1.9 μm).

[0040] (2) Test results like Figure 2 As shown, the CuFeS2 / Ni-g-C3N4 composite catalyst exhibits significantly better algicidal performance than the single-component catalysts (CuFeS2, Ni / g-C3N4) and the control group, making it a highly efficient photocatalytic killer of Microcystis aeruginosa. Dark reaction control experiments confirmed that the killing activity of this composite catalyst is strictly dependent on light irradiation, representing a typical photocatalytic mechanism. The activities of single-component CuFeS2 and Ni / g-C3N4 are both weaker than those of the composite catalyst, indicating that the combination of the two produces a synergistic catalytic effect, significantly improving the separation efficiency of photogenerated carriers or the generation capacity of active species.

[0041] like Figure 3 As shown, the CuFeS2 / Ni-g-C3N4 composite catalyst exhibits significantly better algal toxin degradation performance than the single-component catalysts (CuFeS2, Ni / g-C3N4) and the control group, making it a highly efficient photocatalytic degradation agent for algal toxins. Both single-component CuFeS2 and Ni / g-C3N4 showed extremely weak activity, but the composite catalyst showed a significant increase in activity, demonstrating a synergistic effect that promoted the separation of photogenerated carriers and the removal of reactive oxygen species (such as ·OH and ·O2). - The generation of algal toxins through efficient oxidation and decomposition.

[0042] The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. For those skilled in the art, various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and these variations still fall within the protection scope of the present invention.

Claims

1. A method for synthesizing a nickel-containing carbon nitride-supported chalcopyrite composite material, characterized in that, Includes the following steps: S1. A graphitic carbon nitride precursor is prepared by high-temperature polymerization using a nitrogen-containing carbon-based precursor; subsequently, the graphitic carbon nitride is dispersed in water, ultrasonically treated, and dried to achieve its modification. Modified graphitic carbon nitride was then dispersed in a water-alcohol mixed solution, and nickel chloride solution was added. After stirring in a water bath, washing, and drying, the loading modification was completed, and finally nickel carbon nitride composite material was obtained. S2. Using nickel carbon nitride composite material as a base, disperse it in water; then add copper salt solution, iron salt solution and thiourea solution, and after heating and stirring, carry out hydrothermal reaction on the resulting mixture. After the reaction, collect the precipitate and wash it. After washing and drying, the precipitate is calcined in an inert gas atmosphere to obtain a nickel-containing carbon nitride-supported chalcopyrite composite material.

2. The method for synthesizing a nickel-containing carbon nitride-supported chalcopyrite composite material according to claim 1, characterized in that, The nitrogen-containing carbon-based precursors mentioned in step S1 include urea, melamine, dicyandiamide, or thiourea.

3. The method for synthesizing a nickel-containing carbon nitride-supported chalcopyrite composite material according to claim 1, characterized in that, The high-temperature polymerization in step S1 is carried out at a temperature of 450℃~650℃, a heating rate of 5℃ / min~30℃ / min, and a time of 1~3h; the ultrasonic treatment is carried out at a power of 40~60W for 15~30min.

4. The method for synthesizing a nickel-containing carbon nitride-supported chalcopyrite composite material according to claim 1, characterized in that, In step S1, the ratio of graphitic carbon nitride to nickel chloride solution is 45–55 mg: 7–15 mL, and the concentration of nickel chloride solution is 1.3–1.8 mg / mL.

5. The method for synthesizing a nickel-containing carbon nitride-supported chalcopyrite composite material according to claim 1, characterized in that, The water bath stirring temperature in step S1 is 60℃~80℃, the stirring speed is 7000~9000 rpm / min, and the stirring time is 3~6h.

6. The method for synthesizing a nickel-containing carbon nitride-supported chalcopyrite composite material according to claim 1, characterized in that, The hydrothermal reaction in step S2 is carried out at a temperature of 180℃ to 220℃, with a heating rate of 5℃ to 10℃ and a reaction time of 12h to 18h.

7. The method for synthesizing a nickel-containing carbon nitride-supported chalcopyrite composite material according to claim 1, characterized in that, The calcination treatment in step S2 is carried out at a temperature of 300℃~600℃, a heating rate of 2℃ / min~15℃ / min, and a reaction time of 60min~180min.

8. The method for synthesizing a nickel-containing carbon nitride-supported chalcopyrite composite material according to claim 1, characterized in that, The iron salt in step S2 includes ferric chloride and ferric nitrate, and the copper salt includes copper nitrate and copper chloride; the molar ratio of the copper salt, iron salt, and thiourea is 1:1.0-1.2:2.0-2.

5.

9. The nickel-containing carbon nitride-supported chalcopyrite composite material prepared by the preparation method described in claims 1 to 8.

10. The application of the nickel-containing carbon nitride-supported chalcopyrite composite material of claim 9 in inactivating Microcystis aeruginosa in aquatic environments and / or degrading algal toxins in aquatic environments.

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