A ternary chalcogenide compound composite perovskite catalytic material, a synthesis method and application thereof

Abstract

The application discloses a ternary chalcogenide compound composite perovskite catalytic material and a synthesis method and application thereof, and belongs to the field of photocatalysts. The synthesis method comprises the following steps: adding silver nitrate and indium chloride into anhydrous ethanol, adding thioacetamide, performing a hydrothermal reaction, centrifuging, washing, and drying to obtain the material AgIn5S8; dissolving AgIn5S8, MnCl2.4H2O and citric acid in distilled water, adding La(NO3)3.6H2O, heating and continuously stirring until a gel-like precursor is obtained, performing a hydrothermal reaction, washing, filtering, drying, calcining the obtained composite material, and naturally cooling to obtain the catalytic material AgIn5S8 / LaMnO3. The AgIn5S8 / LaMnO3 photocatalytic system realizes effective degradation of pollutants, generates various active oxidizing substances after reacting with water molecules and dissolved oxygen after excitation by visible light, and degrades the pollutants in the water phase in a high efficiency.

Description

Technical Field

[0001] The present invention belongs to the field of photocatalysts, and in particular relates to a ternary sulfide compound composite perovskite catalytic material, a synthesis method and an application thereof. Background Art

[0002] In the field of photocatalysis, various types of semiconductors have been used to remove organic pollutants from aqueous media. To this end, a growing number of photocatalysts have emerged, including bismuth-based, silver-based, phosphorus-based, titanium dioxide-based, cadmium sulfide-based, peroxide-based, metal-organic framework-based, and g-C₃N₄-based photocatalysts. In recent years, ternary doped semiconductor materials have been widely used in environmental and energy applications related to photocatalysis. Among them, AgIn₅S₄, with its narrow band gap (1.70–1.80 eV) and wide solar absorption range (~700 nm), is a potential visible-light-responsive photocatalyst. However, the rapid charge recombination, low quantum efficiency, and unavoidable photocorrosion of single-component AgIn₅S₄ hinder its practical application. The degradation performance of photocatalysts is primarily determined by charge separation and transport. Furthermore, the oxidation capacity of photocatalysts is constrained by their energy band position, which significantly influences the mineralization and biodegradability of pollutants. Therefore, simultaneously improving the ability to both charge separation and generate oxidative species (hydroxyl radicals, superoxide radicals, sulfate radicals, singlet oxygen, etc.) is crucial for the photocatalytic degradation and mineralization of organic pollutants.

[0003] Among various strategies, constructing heterojunctions in photocatalysts can improve the feasibility and effectiveness of spatial separation of electron-hole pairs and has been proven to be one of the methods for modifying photocatalysts. Appropriately designing the spatial potential difference between semiconductors with matching band structures and electronic energy levels can accelerate the separation and transfer of photogenerated electron-hole pairs, expand the spectral response range, and significantly improve the photocatalytic activity and photochemical stability of heterojunction photocatalysts.

[0004] Lanthanum manganate (LaMnO3), as a typical ABO3 perovskite structure and native p-type semiconductor, has been theoretically and experimentally proven to be an effective photocatalyst, showing unique physical and chemical properties in the field of photocatalytic water oxidation and degradation of organic pollutants, and has the characteristics of low cost and environmental friendliness. In addition, due to its Mn 4+ ↔Mn 3+Due to its reversible reduction performance, LaMnO3 is a candidate catalyst for heterogeneous catalytic processes. However, the narrow band gap of LaMnO3 leads to a high carrier recombination rate, which limits its use in photocatalytic processes. Therefore, coupling LaMnO3 with different semiconductors and tuning the band potential is considered an effective way to hinder the recombination rate and improve photocatalytic activity. The valence band position of LaMnO3 is ~1.95eV and the conduction band position is 0.01eV, while the valence band position of AgIn5S8 is about 1.01eV and the conduction band position is about -0.72eV. The band positions of the two make LaMnO3 and AgIn5S8 theoretically well matched to form a heterojunction.

[0005] Therefore, the present invention develops a ternary chalcogenide composite perovskite catalytic material and synthesizes an AgIn5S8 / LaMnO3 S-type heterojunction, which can photodegrade the pollutant bisphenol A under visible light irradiation. Summary of the Invention

[0006] The purpose of the present invention is to provide a method for synthesizing a ternary sulfide compound composite perovskite catalytic material, so as to prepare a ternary sulfide composite perovskite catalytic material with stronger visible light absorption, higher charge separation efficiency, better stability, reusability, and the ability to achieve photocatalytic degradation of organic pollutants by a simple process.

[0007] Another object of the present invention is to provide a ternary chalcogenide composite perovskite catalytic material.

[0008] Another object of the present invention is to provide an application of a ternary chalcogenide composite perovskite catalytic material.

[0009] The technical solution of the present invention is: (one)

[0011] A method for synthesizing a ternary chalcogenide composite perovskite catalytic material, characterized by comprising the following steps:

[0012] A. Add silver nitrate and indium chloride to anhydrous ethanol and continue stirring for 15-30 minutes, then add thioacetamide and continue stirring for 15-30 minutes, then subject the solution to a hydrothermal reaction. After the reaction is completed, cool to room temperature, collect the resulting product by centrifugation, wash, and then dry to constant weight to obtain the material AgIn5S8;

[0013] B. Dissolve AgIn5S8, MnCl2·4H2O, and citric acid in distilled water and continue stirring for 15-30 minutes. Then add La(NO3)3·6H2O and continue stirring for 15-30 minutes. Heat the solution and continue stirring until a gel-like precursor is obtained. Then, perform a hydrothermal reaction. After the reaction is completed, wash, filter, and dry to constant weight. Finally, calcine the obtained composite material and naturally cool it to obtain the catalytic material AgIn5S8 / LaMnO3.

[0014] As a further improvement of the present invention, in step A, the molar ratio of silver nitrate, indium chloride and thioacetamide is 1:2.5-5:4-8.

[0015] As a further improvement of the present invention, in step A, the temperature of the hydrothermal reaction is 160-200° C., and the time of the hydrothermal reaction is 20-24 h.

[0016] As a further improvement of the present invention, in step B, the mass ratio of AgIn5S8, MnCl2·4H2O, citric acid and La(NO3)3·6H2O is 100:16.8-33.6:31.7-63.4:34.7-69.4.

[0017] As a further improvement of the present invention, in step B, the heating temperature is 70-80° C., and the stirring time is 5-10 minutes.

[0018] As a further improvement of the present invention, in step B, the temperature of the hydrothermal reaction is 180-240° C., and the time of the hydrothermal reaction is 16-20 h.

[0019] As a further improvement of the present invention, in step B, during calcination, the heating rate is 2-10°C / min, the calcination temperature is 600-800°C, the calcination time is 3-5h, and the atmosphere is air. (two)

[0021] A ternary sulfide compound composite perovskite catalytic material is prepared by the above-mentioned synthesis method of the ternary sulfide compound composite perovskite catalytic material.

[0022] AgIn5S8 is a ternary chalcogenide, while LaMnO3 is a perovskite material. The two have similar band gaps of 1.74eV and 1.94eV, respectively, which means that a single material can capture the vast majority of visible light. It is just that the narrow band gap leads to a high recombination rate of bulk carriers in the two. AgIn5S8 and LaMnO3 have matching band structures. Therefore, when the two are combined, the matching energy level structure can transfer the photogenerated electrons of LaMnO3 across the heterojunction interface to AgIn5S8, reducing the recombination of electron-hole pairs and greatly enhancing the spatial interface charge transfer efficiency. The synergistic effect of the two enhances the visible spectrum absorption. The existence of the heterojunction compensates for the problem of unreasonable energy band positions of each other, effectively improving the efficiency of light capture and spatial interface separation, making the S-type heterojunction material able to efficiently degrade pollutants under the action of visible light, and has good stability in the aqueous phase and is recyclable. (three)

[0024] Application of a ternary sulfide compound composite perovskite catalytic material in photocatalytic degradation of pollutants.

[0025] Furthermore, the pollutants include bisphenol A, and also include atrazine, carbamazepine, tetracycline, rhodamine b, etc. Preferably, the AgIn5S8 / LaMnO3 of the present invention has an exceptionally excellent degradation effect on bisphenol A under photocatalytic conditions. On the one hand, the photocatalytic material AgIn5S8 / LaMnO3 is photoexcited to generate photogenerated electrons and photogenerated holes under visible light conditions. The matching energy level position enables the photogenerated electrons of the LaMnO3 conduction band to be transferred across the heterojunction interface to the AgIn5S8 valence band. This S-type charge transport mechanism not only promotes carrier separation, but also retains strong redox ability and promotes space charge transfer. On the other hand, in the presence of a polarizing electric field, the continuous generation of photogenerated electron-hole pairs on the surface of the LaMnO3 material is further induced, which significantly improves the charge separation efficiency.

[0026] The present invention has the following beneficial effects: the ternary chalcogenide AgIn5S8 and the perovskite material LaMnO3 have narrow band gaps and good visible light absorption. However, pure single materials face problems such as rapid charge recombination and photocorrosion, resulting in low activity. The present invention combines AgIn5S8 and LaMnO3 by forming a heterojunction, creating an S-type heterojunction catalytic material—AgIn5S8 / LaMnO3—with enhanced charge separation, an absorption range covering the entire visible spectrum, and higher catalytic activity. Traditional single-component AgIn5S8 and LaMnO3 have good visible light absorption, but their narrow band gaps mean faster in-situ carrier recombination. The two materials possess interdigitated energy band structures. By combining AgIn5S8 and LaMnO3 via a heterojunction, they successfully achieved separation of photogenerated electron-hole pairs at the heterointerface of the AgIn5S8 / LaMnO3 composite photocatalytic nanomaterial, avoiding the electron-hole recombination problem inherent in the band gap of a single nanomaterial. The aligned energy levels of the two materials accelerate the migration and separation of photogenerated charges. The S-type heterojunction allows photogenerated electrons from LaMnO3 to transfer across the heterojunction interface to AgIn5S8 under visible light irradiation, minimizing electron-hole pair recombination in the bulk phase. This effectively enhances charge separation and electron transfer at the heterojunction interface, significantly improving photocatalytic activity. This also mitigates the illogical energy band positions of a single material. Ultimately, the AgIn5S8 / LaMnO3 photocatalytic system achieves effective pollutant degradation. Upon visible light excitation, the LaMnO3 reacts with water molecules and dissolved oxygen to generate a variety of active oxidizing species, effectively degrading pollutants in the aqueous phase. The invention has the characteristics of simple synthesis method, good stability and reusability. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 This is a scanning electron microscope image of AgIn5S8 / LaMnO3 prepared in Example 1 of the present invention;

[0028] Figure 2 Ultraviolet diffuse reflection absorption spectra of AgIn5S8 / LaMnO3, AgIn5S8, and LaMnO3 prepared in Example 1 and Comparative Examples 1 and 2 of the present invention;

[0029] Figure 3 Fourier transform infrared spectra of AgIn5S8 / LaMnO3, AgIn5S8, and LaMnO3 prepared in Example 1 and Comparative Examples 1 and 2 of the present invention;

[0030] Figure 4 This is a performance comparison chart of AgIn5S8 / LaMnO3, AgIn5S8, and LaMnO3 prepared in Example 1 of the present invention and Comparative Examples 1 and 2 for photocatalytic degradation of bisphenol A;

[0031] Figure 5 This is a degradation diagram of the reusability experiment of photocatalytic degradation of bisphenol A by AgIn5S8 / LaMnO3 prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0032] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.

[0033] Example 1

[0034] A method for synthesizing a ternary chalcogenide composite perovskite catalytic material comprises the following steps:

[0035] A. Add 1 mmol of silver nitrate and 5 mmol of indium chloride to 60 mL of anhydrous ethanol and stir continuously at 600 r / min for 15 min. Then add 8 mmol of thioacetamide and continue stirring at 600 r / min for 15 min. Then transfer the solution to a 100 mL polytetrafluoroethylene-lined hydrothermal reactor for hydrothermal reaction. Keep it at 160 ° C for 24 h. After the reaction is completed, cool it to room temperature, collect the obtained product by centrifugation, wash it with deionized water and anhydrous ethanol several times, and then dry it in an oven at 60 ° C to constant weight to obtain the material AgIn5S8;

[0036] B. Dissolve 100 mg of AgIn5S8, 33.6 mg of MnCl2·4H2O, and 63.4 mg of citric acid in 60 mL of distilled water and stir continuously at 600 r / min for 15 min. Then add 69.4 mg of La(NO3)3·6H2O and continue stirring at 600 r / min for 15 min. Heat the solution to 70°C and stir continuously at 600 r / min for 5 min until a gel precursor is obtained. Then transfer it to a 100 mL polytetrafluoroethylene-lined hydrothermal reactor for hydrothermal reaction, maintain it at 210°C for 18 h. After the reaction, wash it with deionized water and anhydrous ethanol, filter it, and dry it in an oven at 60°C to constant weight. Finally, calcinate the obtained composite material at high temperature in a box furnace, heating it to 700°C at 2°C / min and calcining it for 4 h. After natural cooling, the catalytic material AgIn5S8 / LaMnO3 can be obtained.

[0037] Figure 1 This is a scanning electron microscope image of AgIn5S8 / LaMnO3 prepared in this example. Figure 1 As shown, AgIn5S8 / LaMnO3 layered nanosheets stacked on each other to form a nanoblock-like structure. This compact structure is conducive to the rapid transfer of photogenerated electrons between each other.

[0038] Comparative Example 1

[0039] Prepare only AgIn5S8:

[0040] 1 mmol of silver nitrate and 5 mmol of indium chloride were added to 60 mL of anhydrous ethanol and stirred at 600 r / min for 20 min. Then 4 mmol of thioacetamide was added and stirred at 600 r / min for 20 min. The solution was then transferred to a 100 mL polytetrafluoroethylene-lined hydrothermal reactor for hydrothermal reaction, maintained at 200 ° C for 20 h. After the reaction, it was cooled to room temperature, and the product was collected by centrifugation, washed several times with deionized water and anhydrous ethanol, and then dried in an oven at 60 ° C to constant weight to obtain the material AgIn5S8.

[0041] Comparative Example 2

[0042] Prepare only LaMnO3:

[0043] 33.6 mg MnCl2·4H2O and 63.4 mg citric acid were dissolved in 60 mL distilled water and stirred at 600 r / min for 30 min. Then 69.4 mg La(NO3)3·6H2O was added and stirred at 600 r / min for 30 min. The solution was heated to 80°C and stirred at 600 r / min for 7.5 min until a gel precursor was obtained. It was then transferred to a 100 mL polytetrafluoroethylene-lined hydrothermal reactor for hydrothermal reaction, maintained at 240°C for 16 h. After the reaction, it was washed with deionized water and anhydrous ethanol, filtered, and dried in an oven at 60°C to constant weight. Finally, the obtained composite material was calcined at high temperature in a box furnace, heated to 600°C at 5°C / min, and calcined for 5 h. After natural cooling, the catalytic material LaMnO3 was obtained.

[0044] Example 2

[0045] A method for synthesizing a ternary chalcogenide composite perovskite catalytic material comprises the following steps:

[0046] A. 1 mmol silver nitrate and 2.5 mmol indium chloride were added to 60 mL anhydrous ethanol and stirred at 600 r / min for 30 min. Then 4 mmol thioacetamide was added and stirred at 600 r / min for 30 min. The solution was then transferred to a 100 mL polytetrafluoroethylene-lined hydrothermal reactor for hydrothermal reaction at 200 ° C for 20 h. After the reaction was completed, it was cooled to room temperature and the product was collected by centrifugation. It was washed several times with deionized water and anhydrous ethanol and then dried in an oven at 60 ° C to constant weight to obtain the material AgIn5S8.

[0047] B. Dissolve 100 mg of AgIn5S8, 16.8 mg of MnCl2·4H2O, and 31.7 mg of citric acid in 60 mL of distilled water and stir continuously at 600 r / min for 30 min. Then add 34.7 mg of La(NO3)3·6H2O and continue stirring at 600 r / min for 30 min. Heat the solution to 80°C and stir continuously at 600 r / min for 10 min until a gel precursor is obtained. Then transfer it to a 100 mL polytetrafluoroethylene-lined hydrothermal reactor for hydrothermal reaction, maintain it at 180°C for 20 h. After the reaction, wash it with deionized water and anhydrous ethanol, filter it, and dry it in an oven at 60°C to constant weight. Finally, calcinate the obtained composite material at high temperature in a box furnace, heating it to 600°C at 10°C / min and calcining it for 5 h. After natural cooling, the catalytic material AgIn5S8 / LaMnO3 can be obtained.

[0048] Example 3

[0049] A method for synthesizing a ternary chalcogenide composite perovskite catalytic material comprises the following steps:

[0050] A. Add 1 mmol of silver nitrate and 2.5 mmol of indium chloride to 60 mL of anhydrous ethanol and stir continuously at 600 r / min for 30 min. Then add 8 mmol of thioacetamide and continue stirring at 600 r / min for 15 min. Then transfer the solution to a 100 mL polytetrafluoroethylene-lined hydrothermal reactor for hydrothermal reaction. Keep it at 180 ° C for 22 h. After the reaction is completed, cool it to room temperature, collect the obtained product by centrifugation, wash it with deionized water and anhydrous ethanol several times, and then dry it in an oven at 60 ° C to constant weight to obtain the material AgIn5S8;

[0051] B. Dissolve 100 mg of AgIn5S8, 33.6 mg of MnCl2·4H2O, and 31.7 mg of citric acid in 60 mL of distilled water and stir continuously at 600 r / min for 30 min. Then add 69.4 mg of La(NO3)3·6H2O and continue stirring at 600 r / min for 15 min. Heat the solution to 75°C and stir continuously at 600 r / min for 8 min until a gel precursor is obtained. Then transfer it to a 100 mL polytetrafluoroethylene-lined hydrothermal reactor for hydrothermal reaction, maintaining it at 240°C for 16 h. After the reaction, wash it with deionized water and anhydrous ethanol, filter it, and dry it in an oven at 60°C to constant weight. Finally, calcinate the obtained composite material at high temperature in a box furnace, heating it to 800°C at 5°C / min and calcining it for 3 h. After natural cooling, the catalytic material AgIn5S8 / LaMnO3 can be obtained.

[0052] (1) Evaluation of photocatalytic degradation performance

[0053] Bisphenol A photodegradation experiments were conducted on the catalytic materials prepared in Example 1 and Comparative Examples 1 and 2 to evaluate the photodegradation performance of the synthesized AgIn5S8 / LaMnO3 photocatalyst under PMS activation. The specific experiments are as follows:

[0054] The photodegradation process was carried out in a 250 ml custom double-walled quartz beaker with a cooling water circulation system to maintain a constant reaction temperature. The light source was a 300 W xenon lamp (420 < λ < 780 nm) with an average light intensity of 200 mW / cm 2 . Before the reaction started, 50 mg of photocatalyst was dispersed in bisphenol A solution (10 mg / L, 100 mL), and the pH value was controlled at around 7 with 0.1 M hydrochloric acid or sodium hydroxide solution. The suspension was stirred continuously during the entire reaction process. A dark adsorption experiment was performed 30 minutes before illumination to achieve the adsorption-desorption equilibrium between bisphenol A and the photocatalyst. Then, 1 mM PMS was added. During the photodegradation process, 1 mL of the reaction solution was taken out at regular intervals and then passed through a 0.22 μm filter in preparation for ultra-high performance liquid chromatography analysis. The mobile phase was acetonitrile and ultrapure water (volume ratio 50:50) and the detection wavelength was 278 nm. The relative concentration (C / C0) was used to calculate the degradation efficiency.

[0055] Figure 2 The following are the ultraviolet diffuse reflection absorption spectra of AgIn5S8 / LaMnO3, AgIn5S8, and LaMnO3 prepared in Example 1 and Comparative Examples 1 and 2. Figure 2 As shown, the absorption cutoff edges of individual AgIn5S8 and LaMnO3 are approximately 688 and 770 nm, respectively, meaning both materials can absorb the vast majority of visible light. For the composite AgIn5S8 / LaMnO3, the complementary absorption of the two enhances the overall absorption while preserving the intensity of the absorption tail. The absorption cutoff extends to approximately 780 nm, effectively improving the composite's visible light capture efficiency.

[0056] Figure 3 The Fourier transform infrared spectra of AgIn5S8 / LaMnO3, AgIn5S8, and LaMnO3 prepared in Example 1 and Comparative Examples 1 and 2 are shown. For AgIn5S8, the wavelength is 3425cm -1 、1339cm -1 and 1548cm -1 The peaks near the hydroxyl group correspond to the stretching vibrations at 525–700 cm -1 The peak at 610 cm corresponds to the vibration of In-S bond in AgIn5S8. For LaMnO3, it can be seen from the FTIR spectrum of pure LaMnO3 that-1 The presence of a strong absorption band at is attributed to the stretching vibration of the Mn-O bond. For the composite AgIn5S8 / LaMnO3, the FTIR spectrum clearly retains the typical characteristic peaks corresponding to both AgIn5S8 and LaMnO3, indicating that AgIn5S8 / LaMnO3 was successfully synthesized and that the basic structure of the combined AgIn5S8 and LaMnO3 is well maintained.

[0057] Figure 4 The performance comparison chart of photocatalytic degradation of bisphenol A of AgIn5S8 / LaMnO3, AgIn5S8 and LaMnO3 prepared in Example 1 and Comparative Examples 1 and 2 is shown in FIG. Figure 4 As shown in the experimental results, under the conditions of a catalyst dosage of 0.5 g / L, an initial BPA concentration of 10 mg / L, and an initial temperature of room temperature, the degradation efficiencies of the single AgIn5S8 / PMS and LaMnO3 / PMS systems for BPA were 46.38% and 64.42%, respectively, within 25 minutes. This indicates that single-material systems have a certain degree of BPA degradation efficiency under visible light irradiation. However, the narrow band gap leads to a high bulk carrier recombination rate, which prevents the effective utilization of photogenerated electrons. The AgIn5S8 / LaMnO3 / PMS system achieved a BPA removal efficiency of 95.84%, indicating that the S-type heterojunction constructed from the two materials with matching band structures effectively enhances the interfacial charge transfer of photogenerated carriers and suppresses the in situ recombination of photogenerated electron-hole pairs in the two single photocatalysts.

[0058] (2) Continuous degradation experiment

[0059] After the first degradation reaction of the AgIn5S8 / LaMnO3 prepared in Example 1 was completed, the reaction solution was centrifuged and washed, and the recovered catalyst was dried in a freeze dryer for 48 hours, and then placed in the reactor again for the next degradation experiment. Except for the materials, the other degradation reaction conditions were consistent with the setting procedures of the first photocatalytic degradation performance evaluation experiment; after the second reaction was completed, the above steps were repeated to carry out three degradation experiments.

[0060] Figure 5 This is a degradation diagram of the reusability experiment of AgIn5S8 / LaMnO3 photocatalytic degradation of bisphenol A prepared in Example 1. Figure 5 As shown, the degradation efficiency of bisphenol A was above 85% in three consecutive degradation experiments, which indicated that the photocatalytic activity of AgIn5S8 / LaMnO3 photocatalytic nanomaterials remained good after three cycles.

Claims

1. A method for synthesizing a ternary chalcogenide composite perovskite catalytic material, characterized in that The following steps are involved: A. Add silver nitrate and indium chloride to anhydrous ethanol and continue stirring, then add thioacetamide and continue stirring, then subject the solution to a hydrothermal reaction. After the reaction is completed, cool to room temperature, collect the resulting product by centrifugation, wash, and then dry to constant weight to obtain the material AgIn5S8; B. Dissolve AgIn5S8, MnCl2·4H2O, and citric acid in distilled water and continue stirring. Then add La(NO3)3·6H2O and continue stirring. Heat the solution and continue stirring until a gel-like precursor is obtained. Then, perform a hydrothermal reaction. After the reaction is completed, wash, filter, and dry to constant weight. Finally, calcine the obtained composite material and naturally cool it to obtain the catalytic material AgIn5S8 / LaMnO3.

2. The method for synthesizing a ternary chalcogenide composite perovskite catalytic material according to claim 1, characterized in that: In step A, the molar ratio of silver nitrate, indium chloride and thioacetamide is 1:2.5-5:4-8.

3. The method for synthesizing a ternary chalcogenide composite perovskite catalytic material according to claim 1, characterized in that: In step A, the temperature of the hydrothermal reaction is 160-200° C., and the time of the hydrothermal reaction is 20-24 h.

4. The method for synthesizing a ternary chalcogenide composite perovskite catalytic material according to claim 1, characterized in that: In step B, the mass ratio of AgIn5S8, MnCl2·4H2O, citric acid and La(NO3)3·6H2O is 100:16.8-33.6:31.7-63.4:34.7-69.

4.

5. The method for synthesizing a ternary chalcogenide composite perovskite catalytic material according to claim 1, characterized in that: In step B, the heating temperature is 70-80° C., and the stirring time is 5-10 min.

6. The method for synthesizing a ternary chalcogenide composite perovskite catalytic material according to claim 1, characterized in that: In step B, the temperature of the hydrothermal reaction is 180-240° C., and the time of the hydrothermal reaction is 16-20 h.

7. The method for synthesizing a ternary chalcogenide composite perovskite catalytic material according to claim 1, characterized in that: In step B, during calcination, the heating rate is 2-10°C / min, the calcination temperature is 600-800°C, the calcination time is 3-5h, and the atmosphere is air.

8. A ternary chalcogenide composite perovskite catalytic material, characterized by: The catalyst is prepared by the synthesis method of the ternary sulfide compound composite perovskite catalytic material according to any one of claims 1 to 7.

9. Use of the ternary chalcogenide composite perovskite catalytic material according to claim 8 in photocatalytic degradation of pollutants.

10. The use of a ternary chalcogenide composite perovskite catalytic material in photocatalytic degradation of pollutants according to claim 9, characterized in that: The contaminants include bisphenol A.

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