Method for treating antibiotic wastewater by using graphite diacetylene / iron sulfide indium nanocomposite activated persulfate

Abstract

The application discloses a method for treating antibiotic wastewater by using a graphdiyne / ferrous indium sulfide nanocomposite to activate persulfate, and the method is characterized by using the graphdiyne / ferrous indium sulfide nanocomposite as a catalyst to activate persulfate for degrading and treating antibiotic wastewater, wherein the graphdiyne / ferrous indium sulfide nanocomposite comprises ferrous indium sulfide nanoparticles, and the nanoparticles are loaded with graphdiyne nanosheets. The method for treating antibiotic wastewater by using the graphdiyne / ferrous indium sulfide nanocomposite to activate persulfate uses the graphdiyne / ferrous indium sulfide nanocomposite as a catalyst, wherein the nanocomposite has many reactive sites, high catalytic activity and good stability, can efficiently activate persulfate with a smaller amount of catalyst, can efficiently remove antibiotics in wastewater, and has the advantages of low cost, high treatment efficiency, good removal effect, green environmental protection and the like, and therefore, the method has important significance for effectively purifying antibiotic wastewater, has high use value and good application prospect.

Description

Technical Field

[0001] This invention belongs to the field of environmental functional nanomaterials and water pollution control technology, and relates to a method for activating persulfate to treat antibiotic wastewater using graphdiyne / iron indium sulfide nanocomposite materials. Background Technology

[0002] With the widespread use of antibiotics, especially in medical treatment, agriculture, and industrial production, antibiotics play a vital role in treating diseases. However, their overuse and abuse lead to large amounts of unmetabolized antibiotics and their degradation products entering water bodies through sewage discharge and agricultural irrigation, severely polluting water sources. Residual antibiotics in water not only affect water quality but also have profound negative impacts on ecosystems. Aquatic microbial communities may be inhibited or killed by antibiotics, disrupting the balance of the ecosystem and reducing biodiversity. Furthermore, the accumulation of antibiotics promotes the emergence and spread of drug-resistant bacteria. These resistant bacteria enter the food chain or water sources, increasing the risk of infection for humans and animals with drug-resistant pathogens, making the treatment of common diseases more difficult and seriously threatening public health. Therefore, against the backdrop of water scarcity and increasingly severe water pollution, effectively controlling antibiotic pollution in water bodies is urgently needed.

[0003] Persulfate-activated Fenton-like advanced oxidation technology has gradually become an important technical means for treating water pollution due to its excellent pollutant degradation performance. The key is to convert persulfate into highly oxidizing free radicals, especially sulfate free radicals (SO42-), under the activation of energy or catalysts. •- These highly oxidizing free radicals can then be used to degrade pollutants in water. Therefore, developing high-performance Fenton-like catalysts is of paramount importance.

[0004] Metal sulfides, especially bimetallic sulfides, have shown significant advantages in the activation of persulfate due to their unique properties and superior catalytic performance. However, to date, there have been no reports on the activation of persulfate using indium iron sulfide. Nevertheless, there are still some disadvantages to using indium iron sulfide monomers to activate persulfate, such as: (1) the poor electron migration ability of indium iron sulfide monomers, which is not conducive to the activation of persulfate; (2) the relatively few active sites of indium iron sulfide monomers, which leads to low activation efficiency of persulfate and low degradation efficiency of pollutants; and (3) indium iron sulfide particles are prone to agglomeration.

[0005] Therefore, obtaining an iron indium sulfide catalyst with multiple reactive sites, high catalytic activity, and good stability is of great significance for the efficient activation of persulfate and the effective removal of antibiotics from water. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to overcome the shortcomings of the prior art and provide a method for treating antibiotic wastewater by activating persulfate using graphdiyne / iron indium sulfide nanocomposite materials, which is low in cost, high in treatment efficiency, good in removal effect, and environmentally friendly.

[0007] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0008] A method for treating antibiotic wastewater by activating persulfate using graphdiyne / indium iron sulfide nanocomposite material, wherein the method uses graphdiyne / indium iron sulfide nanocomposite material as a catalyst to activate persulfate to degrade antibiotic wastewater; the graphdiyne / indium iron sulfide nanocomposite material comprises indium iron sulfide nanoparticles, wherein graphdiyne nanosheets are loaded on the indium iron sulfide nanoparticles.

[0009] In a further improvement to the above method, the mass ratio of graphdiyne nanosheets to indium iron sulfide nanoparticles in the graphdiyne / indium iron sulfide nanocomposite material is 1 to 16:100.

[0010] In a further improvement to the above method, the mass ratio of graphdiyne nanosheets to indium iron sulfide nanoparticles in the graphdiyne / indium iron sulfide nanocomposite material is 3 to 10:100.

[0011] A further improvement to the above method is that the surface of the indium sulfide nanoparticles exhibits a flower-like structure.

[0012] A further improvement to the above method, the preparation method of the graphdiyne / iron indium sulfide nanocomposite material includes the following steps:

[0013] S1. Obtain graphdiyne;

[0014] S2. The graphdiyne, iron salt, indium salt, thiourea and water obtained in step S1 are mixed and subjected to a hydrothermal reaction to obtain a graphdiyne / iron indium sulfide nanocomposite material.

[0015] The above method can be further improved by step S2 as follows:

[0016] S2-1. Mix graphdiyne with water and disperse by ultrasonication to obtain a graphdiyne dispersion.

[0017] S2-2. Add iron salt, indium salt, and thiourea to the graphdiyne dispersion and stir to obtain the precursor solution;

[0018] S2-3. The precursor solution is subjected to a hydrothermal reaction to obtain a graphdiyne / iron indium sulfide nanocomposite material.

[0019] In a further improvement to the above method, the mass ratio of graphdiyne, iron salt, indium salt, and thiourea is 0.0147–0.2352:0.27:0.5865:0.609.

[0020] In a further improvement to the above method, the iron salt is ferric chloride hexahydrate; and the indium salt is indium chloride tetrahydrate.

[0021] In a further improvement to the above method, in step S2-2, the stirring time is 20 min to 40 min.

[0022] In a further improvement to the above method, in steps S2-3, the temperature of the hydrothermal reaction is 160℃~200℃; the time of the hydrothermal reaction is 600min~800min; after the hydrothermal reaction is completed, the method further includes: washing the product obtained after the hydrothermal reaction three times each with water and anhydrous ethanol, and drying it at 70℃ for 720min.

[0023] In a further improvement to the above method, step S1 of the method for preparing graphdiyne includes the following steps:

[0024] S1-1. Hexabromobenzene, calcium carbide, palladium catalyst, copper catalyst and organic mixed solvent are mixed and refluxed at 80°C for 12 h. Tetrabutylammonium fluoride solution is added and refluxed at 80°C for 1 h. Water and concentrated hydrochloric acid are added and refluxed at 60°C for 35 h to obtain graphdiyne slurry.

[0025] S1-2. The graphdiyne slurry was rotary evaporated at 85℃, and the resulting viscous substance was dispersed in anhydrous ethanol. It was repeatedly eluted with anhydrous ethanol and ammonia to remove organic matter and copper catalyst. The mixture was then refluxed with concentrated hydrochloric acid at 85℃ for 1 hour, filtered, and dried to obtain graphdiyne.

[0026] In a further improvement to the above method, the mass ratio of hexabromobenzene, calcium carbide, palladium catalyst, and copper catalyst is 2:2.4:0.06:1; the palladium catalyst is tetra(triphenylphosphine)palladium; the copper catalyst is cuprous iodide; the mass-to-volume ratio of hexabromobenzene to the organic mixed solvent is 1g:20mL; the organic mixed solvent is a mixture of pyridine, tetrahydrofuran, toluene, and ethyl acetate; the volume ratio of pyridine, tetrahydrofuran, toluene, and ethyl acetate is 4:4:5:4; the mass-to-volume ratio of hexabromobenzene to the tetrabutylammonium fluoride solution is 1g:10mL; the mass-to-volume ratio of hexabromobenzene to water is 1g:20mL; and the mass-to-volume ratio of hexabromobenzene to concentrated hydrochloric acid is 1g:10mL.

[0027] A further improvement to the above method, using graphdiyne / iron indium sulfide nanocomposite material as a catalyst to activate persulfate for the degradation of antibiotic wastewater, includes the following steps: mixing the graphdiyne / iron indium sulfide nanocomposite material and antibiotic wastewater, adding persulfate to carry out a Fenton-like degradation reaction, thereby completing the degradation of antibiotics in the wastewater; the amount of graphdiyne / iron indium sulfide nanocomposite material added is 0.05g to 0.2g per liter of antibiotic wastewater; the amount of persulfate added is 0.01g to 0.1g per liter of antibiotic wastewater.

[0028] In a further improvement to the above method, the persulfate is permonosulfate; the antibiotic in the antibiotic wastewater is tetracycline; and the initial concentration of the antibiotic wastewater is ≤10 mg / L.

[0029] In a further improvement to the above method, the Fenton-like degradation reaction time is 6 min to 15 min.

[0030] Compared with the prior art, the advantages of the present invention are as follows:

[0031] (1) In view of the shortcomings of iron indium sulfide monomers, such as poor electron migration ability, relatively few reactive sites, and easy aggregation, and the resulting defects such as difficulty in efficiently activating persulfate, this invention creatively proposes a method for treating antibiotic wastewater by activating persulfate using graphdiyne / iron indium sulfide nanocomposite materials. The graphdiyne / iron indium sulfide nanocomposite materials are used as catalysts to activate persulfate to degrade antibiotic wastewater. The graphdiyne / iron indium sulfide nanocomposite materials include iron indium sulfide nanoparticles, and graphdiyne nanosheets are loaded on the iron indium sulfide nanoparticles. Compared with iron-indium sulfide monomers, the iron-indium sulfide nanoparticles used in this invention, as the main catalytic material, have the following advantages: (a1) Iron-indium sulfide nanoparticles have a larger specific surface area and a relatively greater number of surface reactive sites. These reactive sites can effectively adsorb and activate persulfate, thereby promoting the reaction and improving activation efficiency; (a2) The large number of sulfur atoms exposed in the iron-indium sulfide nanoparticles can efficiently reduce the high-valence metals generated during the activation of persulfate to low-valence metals. By promoting the effective cycle between high / low-valence metals, persulfate can also be continuously and efficiently activated, thereby effectively improving its degradation performance against antibiotics; (a3) ​​Iron-indium sulfide nanoparticles have good thermal and chemical stability, which allows them to maintain stability over a wide pH range in practical applications. Catalytic activity, adaptable to complex water quality conditions; (a4) Indium iron sulfide nanoparticles have the characteristics of low preparation cost and easy availability. Their materials are abundant and inexpensive, which can reduce the production cost of catalysts and are suitable for large-scale applications. On this basis, graphdiyne nanosheets are loaded onto indium iron sulfide nanoparticles, which brings the following advantages: (b1) The surface of graphdiyne nanosheets is rich in alkyne bonds, which is a high-performance reactive site. Therefore, graphdiyne nanosheets can be used as a co-catalyst for composite materials. When indium iron sulfide nanoparticles and graphdiyne nanosheets are combined, they can jointly improve a large number of reactive sites for composite materials, resulting in better catalytic performance. Not only can it promote the conversion of persulfate into a large number of highly oxidizing sulfate radicals (SO4) with a smaller amount of catalyst, but it can also promote the conversion of persulfate into a large number of highly oxidizing sulfate radicals (SO4) with a smaller amount of catalyst. •-(b2) The surface of graphdiyne nanosheets is rich in alkyne bonds, which are also conducive to their composite with indium iron sulfide, thereby improving the chemical stability of the composite material. At the same time, by loading graphdiyne nanosheets on indium iron sulfide nanoparticles, the aggregation of indium iron sulfide nanoparticles can be effectively prevented, thereby improving the reusability of graphdiyne / indium iron sulfide nanocomposites and reducing processing costs. (b3) As a new type of carbon material, graphdiyne nanosheets have high conductivity and excellent carrier mobility, which can effectively promote the rapid transport of electrons, thereby significantly improving the electron migration rate in indium iron sulfide nanoparticles, and thus significantly improving the activation efficiency of persulfate. (b4) Graphdiyne nanosheets have excellent chemical and thermal stability, and can maintain their structure and performance under extreme environments, providing a stable working environment for nanocomposites, making graphdiyne / indium iron sulfide nanocomposites more adaptable. It is evident that the interaction between indium iron sulfide nanoparticles and graphdiyne nanosheets can effectively increase the number of reactive sites in the graphdiyne / indium iron sulfide nanocomposite material, thereby enhancing its activation capacity and efficiency for persulfate. Furthermore, it can improve the stability of the composite material, improve its reusability in aquatic environments, and reduce treatment costs. Therefore, the graphdiyne / indium iron sulfide nanocomposite material of this invention, composed of indium iron sulfide nanoparticles and graphdiyne nanosheets, exhibits better catalytic performance and stability, enabling efficient activation of persulfate. Consequently, the constructed degradation system can efficiently degrade antibiotics in wastewater. This invention discloses a method for treating antibiotic wastewater by activating persulfate using graphdiyne / indium iron sulfide nanocomposite materials. Using graphdiyne / indium iron sulfide nanocomposite materials, which have multiple reactive sites, high catalytic activity, and good stability, as a catalyst, this method achieves efficient activation of persulfate with a smaller catalyst dosage. This results in the efficient removal of antibiotics from the wastewater. The method offers advantages such as low cost, high treatment efficiency, good removal effect, and environmental friendliness. It is of great significance for the effective purification of antibiotic wastewater, has high practical value, and promising application prospects.

[0032] (2) In this invention, by optimizing the mass ratio of graphdiyne nanosheets and indium iron sulfide nanoparticles in the graphdiyne / indium iron sulfide nanocomposite to 1 to 16:100, especially the mass ratio of the two to 3 to 10:100, a graphdiyne / indium iron sulfide nanocomposite with better catalytic performance and stronger stability can be obtained, which can meet different application requirements.

[0033] (3) In this invention, graphdiyne / iron indium sulfide nanocomposites with excellent Fenton-like properties can be prepared by a simple one-step hydrothermal method. Compared with traditional preparation techniques, the preparation method of this invention has mild conditions, requires no complex equipment, is simple to operate, is environmentally friendly, can be prepared on a large scale, and is convenient for industrial application. At the same time, the graphdiyne / iron indium sulfide nanocomposites prepared in this invention have good dispersibility and can significantly improve the separation and transport efficiency of photogenerated carriers, making it an environmentally friendly catalytic material that can be widely used. Attached Figure Description

[0034] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings.

[0035] Figure 1 The X-ray diffraction patterns of the graphdiyne / iron indium sulfide nanocomposite material (A1), graphdiyne, and iron indium sulfide prepared in Example 1 of this invention are shown.

[0036] Figure 2 Fourier transform infrared spectra of the graphdiyne / iron indium sulfide nanocomposite material (A1), graphdiyne, and iron indium sulfide prepared in Example 1 of this invention.

[0037] Figure 3 This is a scanning electron microscope image of the graphdiyne / iron indium sulfide nanocomposite material (A1) prepared in Example 1 of the present invention.

[0038] Figure 4 The energy dispersive X-ray spectral distribution of the graphdiyne / iron indium sulfide nanocomposite material (A1) prepared in Example 1 of this invention is shown.

[0039] Figure 5 This is a comparison diagram showing the degradation effects of graphdiyne / iron indium sulfide nanocomposites (A1, A2, A3), graphdiyne, and iron indium sulfide on tetracycline in Example 1 of the present invention.

[0040] Figure 6 This is a comparison diagram showing the degradation effects of graphene-acetylene / iron indium sulfide nanocomposite materials (C1, C2), iron indium sulfide, and graphene-acetylene on tetracycline in Example 1 of the present invention. Detailed Implementation

[0041] The present invention will be further described below with reference to the accompanying drawings and specific preferred embodiments, but this does not limit the scope of protection of the present invention.

[0042] In the following embodiments of the present invention, unless otherwise specified, the materials and instruments used are commercially available, the equipment used is conventional equipment, and the data obtained are the average values ​​of more than three repeated experiments.

[0043] Example 1

[0044] A method for treating antibiotic wastewater by activating persulfate using graphdiyne / iron indium sulfide nanocomposite materials, specifically involving the activation of persulfate using graphdiyne / iron indium sulfide nanocomposite materials as a catalyst to degrade antibiotic wastewater, including the following steps:

[0045] 100 mL of a 10 mg / L tetracycline solution was placed in a 250 mL Erlenmeyer flask, and 10 mg of graphdiyne / indium iron sulfide nanocomposite material (A1, A2, A3) was added. The mixture was stirred in the dark for 30 min to ensure uniform mixing and allow the tetracycline to reach adsorption-desorption equilibrium on the material surface. Then, 5 mg of persulfate was added to initiate a Fenton-like degradation reaction for 12 min, thus completing the degradation of tetracycline in the water.

[0046] Control group 1: Graphdiyne was used instead of graphdiyne / indium iron sulfide nanocomposite material (A1), with other conditions being the same.

[0047] Control group 2: Indium iron sulfide was used instead of graphdiyne / indium iron sulfide nanocomposite material (A1), with other conditions being the same.

[0048] Control group 3: Graphdiyne / iron indium sulfide nanocomposite material (C1) was used instead of graphdiyne / iron indium sulfide nanocomposite material (A1), the reaction time was 30 min, and other conditions were the same.

[0049] Control group 4: Graphdiyne / iron indium sulfide nanocomposite material (C2) was used instead of graphdiyne / iron indium sulfide nanocomposite material (A1), the reaction time was 30 min, and other conditions were the same.

[0050] In this embodiment, the graphdiyne / iron indium sulfide nanocomposite material (A1) used includes iron indium sulfide nanoparticles, on which graphdiyne nanosheets are loaded; the mass ratio of graphdiyne nanosheets to iron indium sulfide nanoparticles in the graphdiyne / iron indium sulfide nanocomposite material (A1) is 1:25. The surface of the iron indium sulfide nanoparticles exhibits a flower-like structure.

[0051] In this embodiment, the preparation method of the graphdiyne / iron indium sulfide nanocomposite material (A1) includes the following steps:

[0052] S1. Preparation of graphdiyne, specifically:

[0053] S1-1. Mix 2.00 g hexabromobenzene, 2.40 g calcium carbide, 0.06 g palladium catalyst (tetra(triphenylphosphine)palladium), 1.00 g copper catalyst (cuprous iodide) with 40 mL of an organic mixed solvent (the organic mixed solvent is a mixture of pyridine, tetrahydrofuran, toluene and ethyl acetate, and the volume ratio of pyridine, tetrahydrofuran, toluene and ethyl acetate is 4:4:5:4). Place the mixture in a single-necked flask and reflux at 80 °C for 12 h. Add 20 mL of 1 mol / L tetrabutylammonium fluoride solution (added dropwise from the top of the condenser). Reflux at 80 °C for 1 h. Add 40 mL of deionized water and 20 mL of concentrated hydrochloric acid (added dropwise). Reflux at 60 °C for 35 h to obtain a graphdiyne slurry.

[0054] S1-2. The graphdiyne slurry was rotary evaporated at 85℃ to obtain a viscous substance. The viscous substance was dispersed in anhydrous ethanol and repeatedly eluted with anhydrous ethanol and ammonia to remove high-boiling-point organic matter and copper catalyst. The mixture was then refluxed with concentrated hydrochloric acid at 85℃ for 1 hour, filtered, and dried to obtain graphdiyne.

[0055] S2. The graphdiyne, iron salt, indium salt, thiourea, and water obtained in step S1 are mixed and subjected to a hydrothermal reaction to obtain a graphdiyne / iron indium sulfide nanocomposite material, specifically:

[0056] S2-1. Mix 0.0588g of graphdiyne with 70 mL of water and disperse by ultrasonication to obtain a graphdiyne dispersion.

[0057] S2-2. Add 0.2700 g of ferric salt (ferric chloride hexahydrate), 0.5865 g of indium salt (indium chloride tetrahydrate), and 0.6090 g of thiourea to the graphdiyne dispersion and stir for 30 minutes to obtain the precursor solution.

[0058] S2-3. The precursor solution was transferred to a polytetrafluoroethylene stainless steel reactor and subjected to a hydrothermal reaction at 180°C for 720 min. After the reaction was completed, the obtained solid was washed three times each with water and anhydrous ethanol and dried at 70°C for 720 min to obtain a graphdiyne / iron indium sulfide nanocomposite material, designated A1.

[0059] In this embodiment, the graphdiyne / iron indium sulfide nanocomposite material (A2) used is basically the same as the graphdiyne / iron indium sulfide nanocomposite material (A1), the only difference being that the mass ratio of graphdiyne nanosheets to iron indium sulfide nanoparticles in the graphdiyne / iron indium sulfide nanocomposite material (A2) is 1:100.

[0060] In this embodiment, the preparation method of the graphdiyne / iron indium sulfide nanocomposite (A2) is basically the same as that of the graphdiyne / iron indium sulfide nanocomposite (A1), except that the amount of graphdiyne used in the preparation method of the graphdiyne / iron indium sulfide nanocomposite (A2) is 0.0147 g.

[0061] In this embodiment, the graphdiyne / iron indium sulfide nanocomposite material (A3) used is basically the same as the graphdiyne / iron indium sulfide nanocomposite material (A1), the only difference being that the mass ratio of graphdiyne nanosheets to iron indium sulfide nanoparticles in the graphdiyne / iron indium sulfide nanocomposite material (A3) is 4:25.

[0062] In this embodiment, the preparation method of the graphdiyne / iron indium sulfide nanocomposite (A3) is basically the same as that of the graphdiyne / iron indium sulfide nanocomposite (A1), except that the amount of graphdiyne used in the preparation method of the graphdiyne / iron indium sulfide nanocomposite (A3) is 0.2352 g.

[0063] In this embodiment, the preparation method of indium iron sulfide includes the following steps:

[0064] (1) Mix 0.2700 g of iron salt (ferric chloride hexahydrate), 0.5865 g of indium salt (indium chloride tetrahydrate), 0.6090 g of thiourea with 70 mL of water and stir for 30 minutes to obtain a precursor solution.

[0065] (2) The precursor solution was transferred to a polytetrafluoroethylene stainless steel reactor and subjected to a hydrothermal reaction at 180°C for 720 min. After the reaction was completed, the obtained solid was washed three times with water and three times with anhydrous ethanol and dried at 70°C for 720 min to obtain indium sulfide nanoparticles.

[0066] In this embodiment, the preparation method of the graphene-1,yne / iron-indium sulfide nanocomposite material (C1) is basically the same as that of the graphadiyne / iron-indium sulfide nanocomposite material (A1), except that in the preparation method of the graphene-1,yne / iron-indium sulfide nanocomposite material (C1), graphene-1,yne is used instead of graphadiyne, and the amount of graphene-1,yne is 0.0294 g.

[0067] In this embodiment, the preparation method of the graphene-1,yne / iron-indium sulfide nanocomposite material (C2) is basically the same as that of the graphadiyne / iron-indium sulfide nanocomposite material (A1), except that in the preparation method of the graphene-1,yne / iron-indium sulfide nanocomposite material (C2), graphene-1,yne is used instead of graphadiyne, and the amount of graphene-1,yne is 0.0882 g.

[0068] In this embodiment, the preparation method of graphene-1,2-diene includes the following steps:

[0069] 2 mL of benzene and 35 mL of ethanol were added to a 250 mL stainless steel ball mill jar. Then, 10 g of calcium carbide powder was added to the mixture. The mixture of these three components, along with stainless steel beads, was then added to the jar. The jar was sealed and a vacuum was applied. The jar was then placed in a planetary ball mill and run at 600 rpm for 24 hours (with a 3-minute break every 6 minutes to prevent overheating). The resulting material was then washed 3-5 times with nitric acid and glacial acetic acid. The cleaned material was dried in a vacuum drying oven (60°C). The dried material was then placed in a tube furnace, where the temperature was increased to 260°C at a rate of 5°C / min, and then annealed at 260°C for 2 hours to obtain graphityne.

[0070] Figure 1 The image shows the X-ray diffraction patterns of the graphdiyne / iron indium sulfide nanocomposite material (A1), graphdiyne, and iron indium sulfide prepared in Example 1 of this invention. Figure 1 It can be seen that the graphdiyne / iron indium sulfide nanocomposite material prepared by this invention contains diffraction peaks of both graphdiyne and iron indium sulfide.

[0071] Figure 2 The images show the Fourier transform infrared (FTIR) spectra of the graphdiyne / indium iron sulfide nanocomposite material (A1), graphdiyne, and indium iron sulfide prepared in Example 1 of this invention. Figure 2 It can be seen that the graphdiyne / iron indium sulfide nanocomposite material prepared by the present invention contains absorption peaks of both graphdiyne and iron indium sulfide.

[0072] Figure 3 This is a scanning electron microscope image of the graphdiyne / iron indium sulfide nanocomposite material (A1) prepared in Example 1 of this invention. From... Figure 3 As can be seen, in the graphdiyne / indium iron sulfide nanocomposite material prepared by the present invention, the surface of the indium iron sulfide nanoparticles exhibits a nanoflower-like structure, and many small nanosheets grow on the surface of the indium iron sulfide nanoparticles. These nanosheets are graphdiyne.

[0073] Figure 4 This is the energy-dispersive X-ray spectral distribution of the graphdiyne / iron indium sulfide nanocomposite material (A1) prepared in Example 1 of this invention. Figure 4 It can be seen that the graphdiyne / iron indium sulfide nanocomposite material prepared in this invention contains carbon, iron, indium and sulfur.

[0074] As can be seen from the above results, the graphdiyne / iron indium sulfide nanocomposite material of the present invention has been successfully prepared, and the graphdiyne / iron indium sulfide nanocomposite material prepared by the present invention exhibits better catalytic performance.

[0075] During the Fenton-like degradation reaction, samples were taken, and the concentration of tetracycline in the solution was determined using a UV-Vis spectrophotometer. The degradation efficiency of different materials for tetracycline was calculated, and the results are as follows: Figure 5 and Figure 6 As shown.

[0076] Figure 5 This is a comparison chart showing the degradation effects of graphdiyne / iron indium sulfide nanocomposites (A1, A2, A3), graphdiyne, and iron indium sulfide on tetracycline in Example 1 of this invention. From... Figure 5 It can be seen that the graphdiyne monomer has a poor activation effect on persulfate, which leads to a relatively poor catalytic degradation of tetracycline. After 12 min of reaction, the removal rate of tetracycline is only 10%. Although the catalytic degradation effect of indium iron sulfide nanoparticles on tetracycline is better than that of graphdiyne, its removal rate of tetracycline is less than 50% after 6 min of reaction. This indicates that the indium iron sulfide nanoparticle monomer cannot quickly activate persulfate, and therefore cannot quickly remove tetracycline from water. Unlike other methods, the graphdiyne / indium iron sulfide nanocomposite material used in this invention exhibits a significantly higher removal rate and degradation rate of tetracycline than graphdiyne and indium iron sulfide monomers. Furthermore, the removal rate gradually increases with the increase of graphdiyne mass in the composite material. For example, the graphdiyne / indium iron sulfide nanocomposite materials (A1, A2, A3) all showed a tetracycline removal rate exceeding 60% after 6 minutes of reaction, demonstrating a very high degradation rate. This indicates that the first-order reaction kinetic constant of the composite material formed by combining graphdiyne nanosheets and indium iron sulfide nanoparticles in this invention is also significantly higher than that of the two monomers. Moreover, when the mass ratio of graphdiyne nanosheets to indium iron sulfide nanoparticles is 1:25, the corresponding graphdiyne / indium iron sulfide nanocomposite material (A1) shows a higher removal rate and degradation rate after 12 minutes of reaction. After 8 minutes, the removal rate of tetracycline exceeded 80%, reaching 86%. This indicates that the composite material formed by combining graphdiyne nanosheets and indium iron sulfide nanoparticles in this invention can efficiently activate persulfate and effectively remove antibiotics from wastewater. However, when the content of graphdiyne nanosheets in the composite material continues to increase, the catalytic performance decreases. This is because excessive graphdiyne nanosheets will not form a composite material with indium iron sulfide nanoparticles, and the catalytic performance of graphdiyne monomer is very poor, leading to a decrease in overall catalytic performance. Therefore, in this invention, when the mass ratio of graphdiyne nanosheets to indium iron sulfide nanoparticles is 1–16:100, the constructed graphdiyne / indium iron sulfide nanocomposite material can efficiently activate persulfate and effectively remove antibiotics from wastewater. In particular, when the mass ratio of graphdiyne nanosheets to indium iron sulfide nanoparticles is 3–10:100, the catalytic activity of the graphdiyne / indium iron sulfide nanocomposite material is even better, enabling rapid and thorough removal of antibiotics from water.

[0077] Figure 6 This is a comparison chart showing the degradation effects of graphene-1,2-dimethylamine / iron indium sulfide nanocomposite materials (C1, C2), iron indium sulfide, and graphene-1,2-dimethylamine on tetracycline in Example 1 of this invention. From... Figure 6 It can be seen that the graphene monomer has a poor activation effect on persulfate, which in turn leads to a relatively poor catalytic degradation of tetracycline, with a removal rate of less than 10% of tetracycline after 12 min of reaction. Meanwhile, from... Figure 6 It can also be seen that even when iron-indium nanoparticles are combined with graphene, the resulting graphene / iron-indium sulfide nanocomposite material is still difficult to rapidly activate persulfate and difficult to rapidly degrade tetracycline in water. After 30 minutes of reaction, the removal rate of tetracycline is still less than 80%, which indicates that the catalytic performance of the graphene / iron-indium sulfide nanocomposite material is poor and far inferior to the graphene / iron-indium sulfide nanocomposite material of the present invention.

[0078] In addition, the graphdiyne / iron indium sulfide nanocomposite material prepared in this invention has been used multiple times to activate persulfate and treat antibiotic wastewater. It can efficiently activate persulfate and efficiently remove antibiotics from water, showing excellent stability. By repeatedly treating antibiotic wastewater with the graphdiyne / iron indium sulfide nanocomposite material, the treatment cost of antibiotic wastewater can be significantly reduced, making it easy to promote and use.

[0079] The results above show that, compared with conventional methods, the present invention utilizes graphdiyne / indium iron sulfide nanocomposite materials to activate persulfate for treating antibiotic wastewater. Using graphdiyne / indium iron sulfide nanocomposite materials, which have multiple reactive sites, high catalytic activity, and good stability, as a catalyst, the method achieves efficient activation of persulfate with less catalyst, thereby efficiently removing antibiotics from wastewater. This method has advantages such as low cost, high treatment efficiency, good removal effect, and environmental friendliness. It is of great significance for the effective purification of antibiotic wastewater, has high practical value, and promising application prospects.

[0080] The above embodiments are merely preferred embodiments of the present invention, and the scope of protection of the present invention is not limited to the above embodiments. All technical solutions falling within the scope of the present invention's concept are within the scope of protection of the present invention. It should be noted that for those skilled in the art, improvements and modifications made without departing from the principles of the present invention should also be considered within the scope of protection of the present invention.

Claims

1. A method for activating persulfate treatment of antibiotic wastewater using graphdiyne / iron indium sulfide nanocomposite materials, characterized in that, The method uses a graphdiyne / iron indium sulfide nanocomposite material as a catalyst to activate persulfate for the degradation of antibiotic wastewater; the graphdiyne / iron indium sulfide nanocomposite material comprises iron indium sulfide nanoparticles, on which graphdiyne nanosheets are loaded; the preparation method of the graphdiyne / iron indium sulfide nanocomposite material includes the following steps: S1. Obtain graphdiyne; S2. The graphdiyne, iron salt, indium salt, thiourea and water obtained in step S1 are mixed and subjected to a hydrothermal reaction to obtain a graphdiyne / iron indium sulfide nanocomposite material; the mass ratio of graphdiyne, iron salt, indium salt and thiourea is 0.0147~0.2352∶0.27∶0.5865∶0.

609.

2. The method according to claim 1, characterized in that, The mass ratio of graphdiyne nanosheets to indium iron sulfide nanoparticles in the graphdiyne / indium iron sulfide nanocomposite material is 1–16:

100.

3. The method of claim 2, wherein, The mass ratio of graphdiyne nanosheets to indium iron sulfide nanoparticles in the graphdiyne / indium iron sulfide nanocomposite material is 3 to 10:100; the surface of the indium iron sulfide nanoparticles has a flower-like structure.

4. The method according to claim 3, characterized in that, Step S2 is as follows: S2-1. Mix graphdiyne with water and disperse by ultrasonication to obtain a graphdiyne dispersion. S2-2. Add iron salt, indium salt, and thiourea to the graphdiyne dispersion and stir to obtain the precursor solution; S2-3. The precursor solution is subjected to a hydrothermal reaction to obtain a graphdiyne / iron indium sulfide nanocomposite material.

5. The method of claim 4, wherein, The iron salt is ferric chloride hexahydrate; the indium salt is indium chloride tetrahydrate; In step S2-2, the stirring time is 20 min to 40 min; In steps S2-3, the temperature of the hydrothermal reaction is 160℃~200℃; the time of the hydrothermal reaction is 600min~800min; after the hydrothermal reaction is completed, the product obtained after the hydrothermal reaction is washed 3 times each with water and anhydrous ethanol, and dried at 70℃ for 720min.

6. The method of claim 3, wherein, In step S1, the method for preparing the graphdiyne includes the following steps: S1-1. Hexabromobenzene, calcium carbide, palladium catalyst, and copper catalyst are mixed with an organic mixed solvent and refluxed at 80°C for 12 hours. Tetrabutylammonium fluoride solution is added, and the mixture is refluxed at 80°C for 1 hour. Water and concentrated hydrochloric acid are added, and the mixture is refluxed at 60°C for 35 hours to obtain a graphdiyne slurry. The mass ratio of hexabromobenzene, calcium carbide, palladium catalyst, and copper catalyst is 2:2.4:0.06:

1. The palladium catalyst is tetra(triphenylphosphine)palladium; the copper catalyst is cuprous iodide. The mass-to-volume ratio of hexabromobenzene to the organic mixed solvent is 1 g: 20 mL; the organic mixed solvent is a mixture of pyridine, tetrahydrofuran, toluene, and ethyl acetate; the volume ratio of pyridine, tetrahydrofuran, toluene, and ethyl acetate is 4:4:5:4; the mass-to-volume ratio of hexabromobenzene to the tetrabutylammonium fluoride solution is 1 g: 10 mL; the mass-to-volume ratio of hexabromobenzene to water is 1 g: 20 mL; the mass-to-volume ratio of hexabromobenzene to concentrated hydrochloric acid is 1 g: 10 mL. S1-2. The graphdiyne slurry was rotary evaporated at 85℃, and the resulting viscous substance was dispersed in anhydrous ethanol. It was repeatedly eluted with anhydrous ethanol and ammonia to remove organic matter and copper catalyst. The mixture was then refluxed with concentrated hydrochloric acid at 85℃ for 1 hour, filtered, and dried to obtain graphdiyne.

7. The method according to any one of claims 1 to 6, characterized in that, The degradation treatment of antibiotic wastewater using graphdiyne / iron indium sulfide nanocomposite material as a catalyst to activate persulfate includes the following steps: mixing graphdiyne / iron indium sulfide nanocomposite material and antibiotic wastewater, adding persulfate to carry out a Fenton-like degradation reaction to complete the degradation of antibiotics in the wastewater; the amount of graphdiyne / iron indium sulfide nanocomposite material added is 0.05g to 0.2g per liter of antibiotic wastewater; the amount of persulfate added is 0.01g to 0.1g per liter of antibiotic wastewater.

8. The method of claim 7, wherein, The persulfate is permonosulfate; the antibiotic in the antibiotic wastewater is tetracycline; the initial concentration of the antibiotic wastewater is ≤10mg / L.

9. The method of claim 8, wherein, The Fenton-like degradation reaction takes 6 to 15 minutes.

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