A method for preparing a composite photocatalytic material for degrading sulfamethoxazole

Abstract

This invention provides a method for preparing a composite photocatalytic material for degrading sulfamethoxazole, comprising the following steps: Step [1] loading linear poly[(2,5-dibromo-4-carbonylthiophene)-(2,5-diamidothiophene)] onto the surface of a copper foam matrix; Step [2] converting the linear poly[(2,5-dibromo-4-carbonylthiophene)-(2,5-diamidothiophene)] into crosslinked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)]; Step [3] assembling BiNdO9Mo2 nanocrystals on the surface of the crosslinked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)]. The photocatalytic degradation material prepared by the method of this invention has photocatalytic degradation performance such as a wide absorption spectrum, high photocatalytic activity, and high stability.

Description

Technical Field

[0001] This invention relates to the field of photocatalytic degradation materials for wastewater treatment, and in particular to a method for preparing a composite photocatalytic material for degrading sulfamethoxazole. Background Technology

[0002] In recent years, sulfamethoxazole has ranked first among sulfonamide antibiotics in terms of detection rate and concentration in environmental water bodies. Sulfamethoxazole is relatively stable in water, difficult to degrade, and easily migrates, exhibiting direct biotoxicity. It can lead to bacterial resistance and the spread of resistance genes, posing a serious threat to human health and the ecological environment. Therefore, the effective treatment of wastewater containing sulfamethoxazole has become a critical issue urgently needing to be addressed for my country's sustainable economic development.

[0003] Photocatalytic degradation of antibiotics is based on the principle that under illumination, photocatalytic materials generate photoelectron-hole pairs through photo-generated electron transitions, which then react with the antibiotics adsorbed on the photocatalytic material, leading to antibiotic degradation. Therefore, photocatalytic degradation of antibiotics is a potential method for effectively treating wastewater containing sulfamethoxazole. However, currently used photocatalytic degradation materials have narrow absorption spectra, only capable of photocatalytic degradation under ultraviolet light, resulting in low photocatalytic efficiency and hindering large-scale and efficient industrial-scale treatment. Summary of the Invention

[0004] To overcome the shortcomings of the prior art, the present invention provides a method for preparing a composite photocatalytic material for degrading sulfamethoxazole. The photocatalytic degradation material prepared by this method has photocatalytic degradation performance such as a wide absorption spectrum, high photocatalytic activity and high stability.

[0005] The technical solution adopted by this invention to solve its technical problem is:

[0006] This invention provides a method for preparing a composite photocatalytic material for degrading sulfamethoxazole, comprising the following steps:

[0007] Step [1] Load linear poly[(2,5-dibromo-4-carbonylthiophene)-(2,5-diamidothiophene)] onto the surface of a copper foam matrix;

[0008] Step [2] converts the linear poly[(2,5-dibromo-4-carbonylthiophene)-(2,5-diamidothiophene)] into crosslinked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)];

[0009] Step [3] Assemble BiNdO9Mo2 nanocrystals on the surface of the cross-linked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamide-thiophene)].

[0010] Preferably, step [1] specifically includes the following operations:

[0011] a1. Add 2,5-dibromo-thiophene-3,4-dicarboxylic acid and 5-aminothiophene-2-carboxamide to dimethyl sulfoxide and mix to form a base solution;

[0012] a2. Add 98% concentrated sulfuric acid to deionized water to form an immersion reaction solution with a mass concentration of 2-6%. Immerse the copper foam matrix in the immersion reaction solution. Under an argon atmosphere, add a certain amount of 1,3-bis(diphenylphosphine)propane palladium chloride to the base solution to form a mixture. Then add a certain amount of this mixture to the immersion reaction solution. Heat to 80-120°C under a continuous argon atmosphere and react for 18-22 hours. Cool to room temperature, wash with ethanol, and dry at room temperature for 8-12 hours to obtain copper foam with linear poly[(2,5-dibromo-4-carbonylthiophene)-(2,5-diamidothiophene)] on the surface, denoted as intermediate A.

[0013] Preferably, in step a1, the amount of 2,5-dibromo-thiophene-3,4-dicarboxylic acid added per liter of the base solution is 150-190g and the amount of 5-aminothiophene-2-carboxamide added is 130-170g.

[0014] Preferably, in step a2: the weight of the copper foam substrate immersed in each liter of the soaking reaction solution is 180-240g; the amount of 1,3-bis(diphenylphosphine)propane-palladium chloride added per liter of the base solution is 5-15g; and the volume ratio of the mixture to the soaking reaction solution is 5-7:2-3.

[0015] Preferably, step [2] specifically includes the following operations:

[0016] 4,5-Difluorophenyl-1,2-diamine, triphenylphosphine rhodium chloride, and sodium tetraphenylborate were added to ethanol under an argon atmosphere to form conversion solution A. Intermediate A was immersed in conversion solution A and heated to 50-75°C under a continuous argon atmosphere for 20-28 hours. After cooling to room temperature, the mixture was washed with deionized water and dried at room temperature for 6-10 hours to obtain copper foam with cross-linked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)] on its surface, denoted as intermediate B.

[0017] Preferably, the amount of 4,5-difluorophenyl-1,2-diamine, 5-10g of triphenylphosphine rhodium chloride, and 20-40g of sodium tetraphenylborate added per liter of the conversion solution A is 170-200g; and the weight of intermediate A impregnated in each liter of the conversion solution A is 130-190g.

[0018] Preferably, step [3] specifically includes the following operations:

[0019] c1. Bismuth trioxide, molybdenum trioxide, 68% nitric acid and disodium dihydrogen pyrophosphate are added to deionized water and mixed to form a reaction solution. The intermediate B is immersed in the reaction solution and heated in a water bath to 50-70°C for 5-7 hours to assemble Bi2O9Mo2 precursor on the surface of cross-linked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)] on the surface of copper foam. The composite copper foam product is taken out and dried for 6-8 hours, and is recorded as intermediate C.

[0020] c2. Add neodymium nitrate and ammonium molybdate to deionized water to form conversion solution B. Immerse the intermediate C in the conversion solution B, heat to 150-180℃, react for 3-5 hours, cool to room temperature, and dry the product for 6-8 hours to convert the Bi2O9Mo2 precursor into BiNdO9Mo2 nanocrystals, and finally obtain the composite photocatalytic material.

[0021] Preferably, in step c1, the concentration of nitric acid in the reaction solution is 0.5-1 mol / L, and the amount of bismuth trioxide added per liter of the reaction solution is 80-100 g, the amount of molybdenum trioxide added is 140-180 g, and the amount of disodium dihydrogen pyrophosphate added is 15-40 g; the amount of intermediate B immersed in per liter of the reaction solution is 180-200 g.

[0022] Preferably, in step c2, the amount of neodymium nitrate added per liter of the conversion solution B is 60-110g and the amount of ammonium molybdate added is 160-190g; the weight of intermediate C immersed in per liter of the conversion solution B is 120-160g.

[0023] The positive effects of this invention: The composite photocatalytic degradation material prepared according to the method described in this invention involves synthesizing cross-linked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)] organic matter and assembling BiNdO9Mo2 nanocrystals on the surface of copper foam. The cross-linked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)] is formed by thiophene monomers through conjugated bonds to create a chain structure, thus exhibiting good electrical conductivity, a small band gap, and high electron mobility. The amide groups on its long chains also give it good visible light absorption properties. BiNdO9… Mo2 nanocrystals have an orthorhombic crystal structure and belong to space group Pnma(62). BiNdO9Mo2 nanocrystals have visible light and ultraviolet light photocatalytic activity. In the photocatalytic degradation of sulfamethoxazole, the poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)] / BiNdO9Mo2 crystals supported on the surface of the prepared composite photocatalytic material help to separate photogenerated electrons and holes, which in turn facilitates the generation of a large number of superoxide radicals and hydroxyl radicals. These superoxide radicals and hydroxyl radicals can attack the active sites of sulfamethoxazole, causing it to degrade rapidly.

[0024] In summary, the photocatalytic degradation material prepared according to the present invention has photocatalytic degradation performance such as broad absorption spectrum, high photocatalytic activity and high stability. Attached Figure Description

[0025] Figure 1 This is a schematic diagram of the preparation process of the composite photocatalytic material described in this invention;

[0026] Figure 2 This is a schematic diagram of the structure of the composite photocatalytic material described in this invention;

[0027] Figure 3 This refers to the photocatalytic degradation rate of sulfamethoxazole in simulated wastewater containing sulfamethoxazole treated in Examples 1, 1, and 2 of this invention.

[0028] Figure 4a , 4b 4c are graphs showing the relationship between the number of times sulfamethoxazole was used and the photocatalytic degradation rate of sulfamethoxazole when treating simulated wastewater containing sulfamethoxazole using Examples 1, 1, and 2. Detailed Implementation

[0029] Reference Figure 1 This invention provides a method for preparing a composite photocatalytic material for degrading sulfamethoxazole, comprising the following steps:

[0030] Step [1] involves loading linear poly[(2,5-dibromo-4-carbonylthiophene)-(2,5-diamidothiophene)] onto the surface of a copper foam matrix, specifically including the following operations:

[0031] a1. Add 2,5-dibromo-thiophene-3,4-dicarboxylic acid and 5-aminothiophene-2-carboxamide to dimethyl sulfoxide and mix to form a base solution, wherein the amount of 2,5-dibromo-thiophene-3,4-dicarboxylic acid added per liter of the base solution is 150-190g and the amount of 5-aminothiophene-2-carboxamide added is 130-170g;

[0032] a2. Add 98% concentrated sulfuric acid to deionized water to form an immersion reaction solution with a mass concentration of 2-6%. Immerse the copper foam substrate in the immersion reaction solution (the weight of the copper foam substrate immersed in each liter of the immersion reaction solution is 180-240g). Under an argon atmosphere, add a certain amount of 1,3-bis(diphenylphosphine)propane palladium chloride to the base solution (the amount of 1,3-bis(diphenylphosphine)propane palladium chloride added to each liter of the base solution), mix to form a mixture, and then add a certain amount of this mixture to the immersion solution. The reaction solution (volume ratio of the mixed solution to the soaking reaction solution is 5-7:2-3) is heated to 80-120℃ under a continuous argon atmosphere for 18-22 hours, cooled to room temperature, washed with ethanol, and dried at room temperature for 8-12 hours to obtain copper foam with linear poly[(2,5-dibromo-4-carbonylthiophene)-(2,5-diamidothiophene)] on its surface, denoted as intermediate A; wherein, the structural formula of the linear poly[(2,5-dibromo-4-carbonylthiophene)-(2,5-diamidothiophene)] is:

[0033]

[0034] Step [2] involves converting the linear poly[(2,5-dibromo-4-carbonylthiophene)-(2,5-diamidothiophene)] into crosslinked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)], specifically as follows:

[0035] 4,5-Difluorophenyl-1,2-diamine, triphenylphosphine rhodium chloride, and sodium tetraphenylborate were added to ethanol under an argon atmosphere to form conversion solution A (the amount of 4,5-difluorophenyl-1,2-diamine added to each liter of conversion solution A was 170 g / L). -200g, 5-10g of rhodium triphenylphosphine chloride, and 20-40g of sodium tetraphenylborate were added. The intermediate A was immersed in the conversion solution A (the weight of intermediate A immersed in the conversion solution A was 130-190g). The mixture was heated to 50-75℃ under a continuous argon atmosphere and reacted for 20-28 hours. After cooling to room temperature, it was washed with deionized water and dried at room temperature for 6-10 hours to obtain copper foam with cross-linked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)] on its surface, denoted as intermediate B. The structural formula of the cross-linked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)] is as follows:

[0036]

[0037] Step [3] involves assembling BiNdO9Mo2 nanocrystals on the surface of the cross-linked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)], specifically including the following operations:

[0038] c1. Add bismuth trioxide, molybdenum trioxide, 68% nitric acid and disodium dihydrogen pyrophosphate to deionized water to form a reaction solution (the concentration of nitric acid in the reaction solution is 0.5-1 mol / L, and the amount of bismuth trioxide added per liter of the reaction solution is 80-100 g, the amount of molybdenum trioxide added is 140-180 g, and the amount of disodium dihydrogen pyrophosphate added is 15-40 g). Immerse intermediate B in the reaction solution (the amount of intermediate B immersed in each liter of the reaction solution is 180-200 g), heat in a water bath to 50-70°C, and react for 5-7 hours to assemble Bi2O9Mo2 precursor on the surface of cross-linked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)] on the surface of copper foam. After taking out the composite copper foam product, dry it for 6-8 hours and record it as intermediate C.

[0039] c2. Add neodymium nitrate and ammonium molybdate to deionized water to form conversion solution B (the amount of neodymium nitrate added per liter of conversion solution B is 60-110g and the amount of ammonium molybdate added is 160-190g). Immerse the intermediate C in the conversion solution B (the weight of intermediate C immersed in the conversion solution B is 120-160g). Heat to 150-180℃ and react for 3-5 hours. After cooling to room temperature, dry the product for 6-8 hours to convert the Bi2O9Mo2 precursor into BiNdO9Mo2 nanocrystals, finally obtaining the composite photocatalytic material. Its microstructure diagram is shown below. Figure 2 As shown.

[0040] The preferred embodiments of the present invention will be described below by way of example.

[0041] Example 1

[0042] Preferred embodiment 1 of the present invention provides a method for preparing a composite photocatalytic material for degrading sulfamethoxazole, comprising the following steps:

[0043] Step [1] involves loading linear poly[(2,5-dibromo-4-carbonylthiophene)-(2,5-diamidothiophene)] onto the surface of a copper foam matrix, specifically including the following operations:

[0044] a1. Add 2,5-dibromo-thiophene-3,4-dicarboxylic acid and 5-aminothiophene-2-carboxamide to dimethyl sulfoxide and mix to form a base solution, wherein the amount of 2,5-dibromo-thiophene-3,4-dicarboxylic acid added per liter of the base solution is 180 g and the amount of 5-aminothiophene-2-carboxamide added per liter of the base solution is 160 g.

[0045] a2. Add 98% concentrated sulfuric acid to deionized water to form an immersion reaction solution with a sulfuric acid mass fraction of 4%. Immerse the copper foam matrix in the immersion reaction solution (the weight of the copper foam matrix immersed in each liter of the immersion reaction solution is 220g). Under an argon atmosphere, add a certain amount of 1,3-bis(diphenylphosphine)propane palladium chloride to the base solution (the amount of 1,3-bis(diphenylphosphine)propane palladium chloride added to each liter of the base solution), mix to form a mixture, and then add a certain amount of the mixture to the immersion reaction solution (the volume ratio of the mixture to the immersion reaction solution is 7:2). Heat to 110°C under a continuous argon atmosphere and react for 21 hours. Cool to room temperature, wash with ethanol, and dry at room temperature for 10 hours to obtain copper foam with linear poly[(2,5-dibromo-4-carbonylthiophene)-(2,5-diamidothiophene)] on the surface, denoted as intermediate A.

[0046] Step [2] involves converting the linear poly[(2,5-dibromo-4-carbonylthiophene)-(2,5-diamidothiophene)] into crosslinked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)], specifically as follows:

[0047] 4,5-Difluorophenyl-1,2-diamine, triphenylphosphine rhodium chloride, and tetraphenylborate sodium were added to ethanol under an argon atmosphere to form conversion solution A (the amount of 4,5-difluorophenyl-1,2-diamine, triphenylphosphine rhodium chloride, and tetraphenylborate sodium added per liter of conversion solution A was 190 g, 8 g, and 30 g respectively). Intermediate A was immersed in conversion solution A (the weight of intermediate A immersed in conversion solution A was 180 g). The mixture was heated to 70°C under a continuous argon atmosphere and reacted for 22 hours. After cooling to room temperature, it was washed with deionized water and dried at room temperature for 8 hours to obtain copper foam with cross-linked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)] on its surface, which was designated as intermediate B.

[0048] Step [3] involves assembling BiNdO9Mo2 nanocrystals on the surface of the cross-linked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)], specifically including the following operations:

[0049] c1. Bismuth trioxide, molybdenum trioxide, nitric acid with a mass fraction of 68% and disodium dihydrogen pyrophosphate are added to deionized water to form a reaction solution (the concentration of nitric acid in the reaction solution is 0.8 mol / L, and the amount of bismuth trioxide, molybdenum trioxide, and disodium dihydrogen pyrophosphate added per liter of the reaction solution is 90 g, 170 g, and 30 g). The intermediate B is immersed in the reaction solution (the amount of intermediate B immersed in each liter of the reaction solution is 190 g), heated to 60°C in a water bath, and reacted for 6 hours to assemble Bi2O9Mo2 precursor on the surface of cross-linked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)] on the surface of copper foam. The composite copper foam product is taken out and dried for 7 hours, and is recorded as intermediate C.

[0050] c2. Neodymium nitrate and ammonium molybdate were added to deionized water to form conversion solution B (100g of neodymium nitrate and 190g of ammonium molybdate were added per liter of conversion solution B). The intermediate C was immersed in conversion solution B (150g of intermediate C was immersed per liter of conversion solution B). The mixture was heated to 170°C and reacted for 4 hours. After cooling to room temperature, the product was dried for 7 hours to convert the Bi2O9Mo2 precursor into BiNdO9Mo2 nanocrystals, and the composite photocatalytic material (copper foam supported poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)] / BiNdO9Mo2 nanocrystals) was finally obtained, which is referred to as Example 1.

[0051] Comparative Example 1

[0052] Comparative Example 1 provides a method for preparing a composite photocatalytic material for degrading sulfamethoxazole, comprising the following steps:

[0053] Step [1] involves loading linear poly[(2,5-dibromo-4-carbonylthiophene)-(2,5-diamidothiophene)] onto the surface of a copper foam matrix, specifically including the following operations:

[0054] a1. 2,5-Dibromo-thiophene-3,4-dicarboxylic acid and 5-aminothiophene-2-carboxamide are added to dimethyl sulfoxide and mixed to form a base solution, wherein the amount of 2,5-dibromo-thiophene-3,4-dicarboxylic acid added per liter of the base solution is 160 g and the amount of 5-aminothiophene-2-carboxamide added is 140 g.

[0055] a2. Add 98% concentrated sulfuric acid to deionized water to form a 4% (w / w) soaking reaction solution. Immerse the copper foam matrix in the soaking reaction solution (the weight of the copper foam matrix immersed in each liter of the soaking reaction solution is 220g). Under an argon atmosphere, add a certain amount of 1,3-bis(diphenylphosphine)propane palladium chloride to the base solution (the amount of 1,3-bis(diphenylphosphine)propane palladium chloride added to each liter of the base solution), mix to form a mixture, and then add a certain amount of the mixture to the soaking reaction solution (the volume ratio of the mixture to the soaking reaction solution is 5:2). Heat to 90°C under a continuous argon atmosphere and react for 20 hours. Cool to room temperature, wash with ethanol, and dry at room temperature for 10 hours to obtain copper foam with linear poly[(2,5-dibromo-4-carbonylthiophene)-(2,5-diamidothiophene)] on the surface, denoted as intermediate A.

[0056] Step [2] involves assembling BiNdO9Mo2 nanocrystals on the surface of the linear poly[(2,5-dibromo-4-carbonylthiophene)-(2,5-diamidothiophene)], specifically including the following operations:

[0057] c1. Bismuth trioxide, molybdenum trioxide, nitric acid with a mass fraction of 68% and disodium dihydrogen pyrophosphate are added to deionized water to form a reaction solution (the concentration of nitric acid in the reaction solution is 0.75 mol / L, and the amount of bismuth trioxide added per liter of the reaction solution is 90 g, the amount of molybdenum trioxide added is 170 g, and the amount of disodium dihydrogen pyrophosphate added is 30 g). The intermediate A is immersed in the reaction solution (the amount of intermediate A immersed in each liter of the reaction solution is 190 g), heated to 60°C in a water bath, and reacted for 6 hours to assemble Bi2O9Mo2 precursor on the surface of linear poly[(2,5-dibromo-4-carbonylthiophene)-(2,5-diamidothiophene)] on the surface of copper foam. After taking out the composite copper foam product, it is dried for 7 hours and recorded as intermediate C.

[0058] c2. Neodymium nitrate and ammonium molybdate were added to deionized water to form conversion solution B (80g of neodymium nitrate and 170g of ammonium molybdate were added per liter of conversion solution B). The intermediate C was immersed in conversion solution B (140g of intermediate C was immersed per liter of conversion solution B). The mixture was heated to 160°C and reacted for 4 hours. After cooling to room temperature, the product was dried for 7 hours to convert the Bi2O9Mo2 precursor into BiNdO9Mo2 nanocrystals, and finally the composite photocatalytic material (copper foam supported linear poly[(2,5-dibromo-4-carbonylthiophene)-(2,5-diamidothiophene)] / BiNdO9Mo2 nanocrystals) was obtained, which was designated as Comparative Example 1.

[0059] Comparative Example 2

[0060] Comparative Example 2 provides a method for preparing a composite photocatalytic material for degrading sulfamethoxazole, comprising the following steps:

[0061] Step [1] involves loading linear poly[(2,5-dibromo-4-carbonylthiophene)-(2,5-diamidothiophene)] onto the surface of a copper foam matrix, specifically including the following operations:

[0062] a1. Add 2,5-dibromo-thiophene-3,4-dicarboxylic acid and 5-aminothiophene-2-carboxamide to dimethyl sulfoxide and mix to form a base solution, wherein the amount of 2,5-dibromo-thiophene-3,4-dicarboxylic acid added per liter of the base solution is 180 g and the amount of 5-aminothiophene-2-carboxamide added per liter of the base solution is 160 g.

[0063] a2. Add 98% concentrated sulfuric acid to deionized water to form a 5% (w / w) soaking reaction solution. Immerse the copper foam matrix in the soaking reaction solution (200g of copper foam matrix is ​​immersed in each liter of the soaking reaction solution). Under an argon atmosphere, add a certain amount of 1,3-bis(diphenylphosphine)propane palladium chloride to the base solution (10g of 1,3-bis(diphenylphosphine)propane palladium chloride is added to each liter of the base solution). Mix to form a mixture. Then add a certain amount of the mixture to the soaking reaction solution (the volume ratio of the mixture to the soaking reaction solution is 7:3). Heat to 100°C under a continuous argon atmosphere and react for 21 hours. Cool to room temperature, wash with ethanol, and dry at room temperature for 10 hours to obtain copper foam with linear poly[(2,5-dibromo-4-carbonylthiophene)-(2,5-diamidothiophene)] on the surface, denoted as intermediate A.

[0064] Step [2] involves converting the linear poly[(2,5-dibromo-4-carbonylthiophene)-(2,5-diamidothiophene)] into crosslinked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)], specifically as follows:

[0065] 4,5-Difluorophenyl-1,2-diamine, triphenylphosphine rhodium chloride, and tetraphenylborate sodium were added to ethanol under an argon atmosphere to form conversion solution A (the amount of 4,5-difluorophenyl-1,2-diamine, triphenylphosphine rhodium chloride, and tetraphenylborate sodium added per liter of conversion solution A was 190 g, 8 g, and 30 g respectively). The intermediate A was immersed in conversion solution A (the weight of intermediate A immersed in conversion solution A was 150 g). The mixture was heated to 65°C under a continuous argon atmosphere and reacted for 22 hours. After cooling to room temperature, the mixture was washed with deionized water and dried at room temperature for 8 hours to obtain copper foam with cross-linked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)] on its surface, which was designated as Comparative Example 2.

[0066] To analyze the absorption spectrum characteristics, photocatalytic activity, and photocatalytic degradation removal rate of sulfamethoxazole-containing wastewater treated by Examples 1, Comparative Example 1, and Comparative Example 2, 0.5 g of sulfamethoxazole was dissolved in 50 mL of methanol to form a mother liquor. This mother liquor was then added to deionized water to form simulated sulfamethoxazole-containing wastewater with a concentration of 10 mg / L. 100 mL of the simulated sulfamethoxazole-containing wastewater was poured into each beaker, and 10 g of each of Examples 1, Comparative Example 1, and Comparative Example 2 were added to each beaker. Using a xenon lamp source at a working current of 22 A and a working voltage of 20 V, Comparative Example 1 was irradiated with ultraviolet light (λ = 360 nm) and visible light (λ = 550 nm) for one hour. The residual concentration of sulfamethoxazole was analyzed by high-performance liquid chromatography (HPLC), and the photocatalytic degradation rate of sulfamethoxazole in the wastewater was calculated. The results are as follows: Figure 3 As shown in the figure, the photocatalytic degradation rates of sulfamethoxazole under ultraviolet and visible light irradiation in Example 1 reached 99% and 91%, respectively. In Comparative Example 1, the photocatalytic degradation rates under ultraviolet and visible light irradiation were 87% and 76%, respectively. In Comparative Example 2, the photocatalytic degradation rates under ultraviolet and visible light irradiation were only 42% and 34%, respectively. Under the aforementioned treatment conditions and times, the relationships between the number of uses and the photocatalytic degradation rate of sulfamethoxazole after repeated use of Example 1, Comparative Example 1, and Comparative Example 2 are as follows: Figure 4a As shown in Figure -c, it can be seen from the figure that the photocatalytic degradation rate of sulfamethoxazole in the simulated sulfamethoxazole-containing wastewater under the fifth treatment under ultraviolet and visible light conditions in Example 1 can still reach 94% and 88%, respectively; however, the photocatalytic degradation rate of sulfamethoxazole in the simulated sulfamethoxazole-containing wastewater under the fifth treatment in Comparative Examples 1 and 2 is significantly reduced.

[0067] In summary, the photocatalytic degradation material prepared according to the present invention has the properties of photocatalytic degradation of sulfamethoxazole with a wide absorption spectrum, high photocatalytic activity and high stability.

[0068] To illustrate this further in detail, three more embodiments are provided below.

[0069] Example 2

[0070] Preferred embodiment 2 of the present invention provides a method for preparing a composite photocatalytic material for degrading sulfamethoxazole, comprising the following steps:

[0071] Step [1] involves loading linear poly[(2,5-dibromo-4-carbonylthiophene)-(2,5-diamidothiophene)] onto the surface of a copper foam matrix, specifically including the following operations:

[0072] a1. 2,5-Dibromo-thiophene-3,4-dicarboxylic acid and 5-aminothiophene-2-carboxamide are added to dimethyl sulfoxide and mixed to form a base solution, wherein the amount of 2,5-dibromo-thiophene-3,4-dicarboxylic acid added per liter of the base solution is 150 g and the amount of 5-aminothiophene-2-carboxamide added is 130 g.

[0073] a2. Add 98% concentrated sulfuric acid to deionized water to form a 2% (w / w) soaking reaction solution. Immerse the copper foam matrix in the soaking reaction solution (the weight of the copper foam matrix immersed in each liter of the soaking reaction solution is 180g). Under an argon atmosphere, add a certain amount of 1,3-bis(diphenylphosphine)propane palladium chloride to the base solution (the amount of 1,3-bis(diphenylphosphine)propane palladium chloride added to each liter of the base solution), mix to form a mixture, and then add a certain amount of the mixture to the soaking reaction solution (the volume ratio of the mixture to the soaking reaction solution is 5:3). Heat to 120°C under a continuous argon atmosphere and react for 18 hours. Cool to room temperature, wash with ethanol, and dry at room temperature for 12 hours to obtain copper foam with linear poly[(2,5-dibromo-4-carbonylthiophene)-(2,5-diamidothiophene)] on the surface, denoted as intermediate A.

[0074] Step [2] involves converting the linear poly[(2,5-dibromo-4-carbonylthiophene)-(2,5-diamidothiophene)] into crosslinked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)], specifically as follows:

[0075] 4,5-Difluorophenyl-1,2-diamine, triphenylphosphine rhodium chloride, and tetraphenylborate sodium were added to ethanol under an argon atmosphere to form conversion solution A (the amount of 4,5-difluorophenyl-1,2-diamine, triphenylphosphine rhodium chloride, and tetraphenylborate sodium added per liter of conversion solution A was 170 g, 5 g, and 40 g respectively). Intermediate A was immersed in conversion solution A (the weight of intermediate A immersed in conversion solution A was 190 g). The mixture was heated to 75°C under a continuous argon atmosphere and reacted for 20 hours. After cooling to room temperature, it was washed with deionized water and dried at room temperature for 10 hours to obtain copper foam with cross-linked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)] on its surface, which was designated as intermediate B.

[0076] Step [3] involves assembling BiNdO9Mo2 nanocrystals on the surface of the cross-linked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)], specifically including the following operations:

[0077] c1. Bismuth trioxide, molybdenum trioxide, nitric acid with a mass fraction of 68% and disodium dihydrogen pyrophosphate are added to deionized water to form a reaction solution (the concentration of nitric acid in the reaction solution is 1 mol / L, and the amount of bismuth trioxide added per liter of the reaction solution is 100 g, the amount of molybdenum trioxide added is 140 g, and the amount of disodium dihydrogen pyrophosphate added is 15 g). The intermediate B is immersed in the reaction solution (the amount of intermediate B immersed per liter of the reaction solution is 180 g), heated to 70°C in a water bath, and reacted for 5 hours to assemble Bi2O9Mo2 precursor on the surface of cross-linked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)] on the surface of copper foam. The composite copper foam product is taken out and dried for 8 hours, and is recorded as intermediate C.

[0078] c2. Neodymium nitrate and ammonium molybdate are added to deionized water to form conversion solution B (the amount of neodymium nitrate added per liter of conversion solution B is 110g and the amount of ammonium molybdate added is 160g). The intermediate C is immersed in the conversion solution B (the weight of intermediate C immersed in each liter of conversion solution B is 120g). The mixture is heated to 150°C and reacted for 5 hours. After cooling to room temperature, the product is dried for 8 hours to convert the Bi2O9Mo2 precursor into BiNdO9Mo2 nanocrystals, and finally the composite photocatalytic material is obtained.

[0079] Example 3

[0080] Preferred embodiment 3 of the present invention provides a method for preparing a composite photocatalytic material for degrading sulfamethoxazole, comprising the following steps:

[0081] Step [1] involves loading linear poly[(2,5-dibromo-4-carbonylthiophene)-(2,5-diamidothiophene)] onto the surface of a copper foam matrix, specifically including the following operations:

[0082] a1. 2,5-Dibromo-thiophene-3,4-dicarboxylic acid and 5-aminothiophene-2-carboxamide are added to dimethyl sulfoxide and mixed to form a base solution, wherein the amount of 2,5-dibromo-thiophene-3,4-dicarboxylic acid added per liter of the base solution is 190 g and the amount of 5-aminothiophene-2-carboxamide added is 170 g.

[0083] a2. Add 98% concentrated sulfuric acid to deionized water to form a 6% (w / w) soaking reaction solution. Immerse the copper foam matrix in the soaking reaction solution (the weight of the copper foam matrix immersed in each liter of the soaking reaction solution is 240g). Under an argon atmosphere, add a certain amount of 1,3-bis(diphenylphosphine)propane palladium chloride to the base solution (the amount of 1,3-bis(diphenylphosphine)propane palladium chloride added to each liter of the base solution), mix to form a mixture, and then add a certain amount of the mixture to the soaking reaction solution (the volume ratio of the mixture to the soaking reaction solution is 7:2). Heat to 80°C under a continuous argon atmosphere and react for 22 hours. Cool to room temperature, wash with ethanol, and dry at room temperature for 8 hours to obtain copper foam with linear poly[(2,5-dibromo-4-carbonylthiophene)-(2,5-diamidothiophene)] on the surface, denoted as intermediate A.

[0084] Step [2] involves converting the linear poly[(2,5-dibromo-4-carbonylthiophene)-(2,5-diamidothiophene)] into crosslinked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)], specifically as follows:

[0085] 4,5-Difluorophenyl-1,2-diamine, triphenylphosphine rhodium chloride, and sodium tetraphenylborate were added to ethanol under an argon atmosphere to form conversion solution A (the amount of 4,5-difluorophenyl-1,2-diamine added per liter of conversion solution A was 200g, the amount of triphenylphosphine rhodium chloride added was 10g, and the amount of sodium tetraphenylborate added was 20g). The intermediate A was immersed in conversion solution A (the weight of intermediate A immersed in conversion solution A was 130g). The mixture was heated to 50°C under a continuous argon atmosphere and reacted for 28 hours. After cooling to room temperature, the mixture was washed with deionized water and dried at room temperature for 6 hours to obtain copper foam with cross-linked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)] on its surface, which was designated as intermediate B.

[0086] Step [3] involves assembling BiNdO9Mo2 nanocrystals on the surface of the cross-linked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)], specifically including the following operations:

[0087] c1. Bismuth trioxide, molybdenum trioxide, nitric acid with a mass fraction of 68% and disodium dihydrogen pyrophosphate are added to deionized water to form a reaction solution (the concentration of nitric acid in the reaction solution is 0.5 mol / L, and the amount of bismuth trioxide added per liter of the reaction solution is 80 g, the amount of molybdenum trioxide added is 180 g, and the amount of disodium dihydrogen pyrophosphate added is 40 g). The intermediate B is immersed in the reaction solution (the amount of intermediate B immersed in each liter of the reaction solution is 200 g), heated to 50°C in a water bath, and reacted for 7 hours to assemble Bi2O9Mo2 precursor on the surface of cross-linked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)] on the surface of copper foam. After taking out the composite copper foam product, it is dried for 6 hours and recorded as intermediate C.

[0088] c2. Add neodymium nitrate and ammonium molybdate to deionized water to form conversion solution B (the amount of neodymium nitrate added per liter of conversion solution B is 60g and the amount of ammonium molybdate added is 190g). Immerse the intermediate C in the conversion solution B (the weight of intermediate C immersed in each liter of conversion solution B is 160g), heat to 180°C, react for 3 hours, cool to room temperature, and dry the product for 6 hours to convert the Bi2O9Mo2 precursor into BiNdO9Mo2 nanocrystals, and finally obtain the composite photocatalytic material.

[0089] Example 4

[0090] Preferred embodiment 4 of the present invention provides a method for preparing a composite photocatalytic material for degrading sulfamethoxazole, comprising the following steps:

[0091] Step [1] involves loading linear poly[(2,5-dibromo-4-carbonylthiophene)-(2,5-diamidothiophene)] onto the surface of a copper foam matrix, specifically including the following operations:

[0092] a1. 2,5-Dibromo-thiophene-3,4-dicarboxylic acid and 5-aminothiophene-2-carboxamide are added to dimethyl sulfoxide and mixed to form a base solution, wherein the amount of 2,5-dibromo-thiophene-3,4-dicarboxylic acid added per liter of the base solution is 170 g and the amount of 5-aminothiophene-2-carboxamide added per liter of the base solution is 150 g.

[0093] a2. Add 98% concentrated sulfuric acid to deionized water to form a 4% (w / w) soaking reaction solution. Immerse the copper foam matrix in the soaking reaction solution (the weight of the copper foam matrix immersed in each liter of the soaking reaction solution is 210g). Under an argon atmosphere, add a certain amount of 1,3-bis(diphenylphosphine)propane palladium chloride to the base solution (the amount of 1,3-bis(diphenylphosphine)propane palladium chloride added to each liter of the base solution), mix to form a mixture, and then add a certain amount of the mixture to the soaking reaction solution (the volume ratio of the mixture to the soaking reaction solution is 5:3). Heat to 100°C under a continuous argon atmosphere and react for 20 hours. Cool to room temperature, wash with ethanol, and dry at room temperature for 10 hours to obtain copper foam with linear poly[(2,5-dibromo-4-carbonylthiophene)-(2,5-diamidothiophene)] on the surface, denoted as intermediate A.

[0094] Step [2] involves converting the linear poly[(2,5-dibromo-4-carbonylthiophene)-(2,5-diamidothiophene)] into crosslinked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)], specifically as follows:

[0095] 4,5-Difluorophenyl-1,2-diamine, triphenylphosphine rhodium chloride, and tetraphenylborate sodium were added to ethanol under an argon atmosphere to form conversion solution A (the amount of 4,5-difluorophenyl-1,2-diamine, triphenylphosphine rhodium chloride, and tetraphenylborate sodium added per liter of conversion solution A was 185g, 8g, and 30g respectively). Intermediate A was immersed in conversion solution A (the weight of intermediate A immersed in conversion solution A was 160g). The mixture was heated to 65°C under a continuous argon atmosphere and reacted for 24 hours. After cooling to room temperature, it was washed with deionized water and dried at room temperature for 8 hours to obtain copper foam with cross-linked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)] on its surface, which was designated as intermediate B.

[0096] Step [3] involves assembling BiNdO9Mo2 nanocrystals on the surface of the cross-linked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)], specifically including the following operations:

[0097] c1. Bismuth trioxide, molybdenum trioxide, nitric acid with a mass fraction of 68% and disodium dihydrogen pyrophosphate are added to deionized water to form a reaction solution (the concentration of nitric acid in the reaction solution is 0.8 mol / L, and the amount of bismuth trioxide added per liter of the reaction solution is 90 g, the amount of molybdenum trioxide added is 160 g, and the amount of disodium dihydrogen pyrophosphate added is 29 g). The intermediate B is immersed in the reaction solution (the amount of intermediate B immersed in each liter of the reaction solution is 190 g), heated to 60°C in a water bath, and reacted for 6 hours to assemble Bi2O9Mo2 precursor on the surface of cross-linked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)] on the surface of copper foam. The composite copper foam product is taken out and dried for 7 hours, and is recorded as intermediate C.

[0098] c2. Neodymium nitrate and ammonium molybdate are added to deionized water to form conversion solution B (85g of neodymium nitrate and 175g of ammonium molybdate are added per liter of conversion solution B). The intermediate C is immersed in conversion solution B (140g of intermediate C is immersed per liter of conversion solution B). The mixture is heated to 165°C and reacted for 4 hours. After cooling to room temperature, the product is dried for 7 hours to convert the Bi2O9Mo2 precursor into BiNdO9Mo2 nanocrystals, thus obtaining the composite photocatalytic material.

[0099] The above description is only a preferred embodiment of the present invention. It should be understood that the above description of the embodiments is only for the purpose of helping to understand the method and core idea of ​​the present invention, and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, etc. made within the idea and principle of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a composite photocatalytic material for degrading sulfamethoxazole, characterized in that, It includes the following steps: Step [1] Load linear poly[(2,5-dibromo-4-carbonylthiophene)-(2,5-diamidothiophene)] onto the surface of a copper foam matrix; Step [2] converts the linear poly[(2,5-dibromo-4-carbonylthiophene)-(2,5-diamidothiophene)] into crosslinked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)]; Step [3] Assemble BiNdO9Mo2 nanocrystals on the surface of the cross-linked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamide-thiophene)].

2. The method for preparing a composite photocatalytic material for degrading sulfamethoxazole according to claim 1, characterized in that, The steps [1] specifically include the following operations: a1. Add 2,5-dibromo-thiophene-3,4-dicarboxylic acid and 5-aminothiophene-2-carboxamide to dimethyl sulfoxide and mix to form a base solution; a2. Add 98% concentrated sulfuric acid to deionized water to form an immersion reaction solution with a mass concentration of 2-6%. Immerse the copper foam matrix in the immersion reaction solution. Under an argon atmosphere, add a certain amount of 1,3-bis(diphenylphosphine)propane palladium chloride to the base solution to form a mixture. Then add a certain amount of this mixture to the immersion reaction solution. Heat to 80-120°C under a continuous argon atmosphere and react for 18-22 hours. Cool to room temperature, wash with ethanol, and dry at room temperature for 8-12 hours to obtain copper foam with linear poly[(2,5-dibromo-4-carbonylthiophene)-(2,5-diamidothiophene)] on the surface, denoted as intermediate A.

3. The method for preparing a composite photocatalytic material for degrading sulfamethoxazole according to claim 2, characterized in that: In step a1, the amount of 2,5-dibromo-thiophene-3,4-dicarboxylic acid added per liter of the base solution is 150-190g and the amount of 5-aminothiophene-2-carboxamide added is 130-170g.

4. The method for preparing a composite photocatalytic material for degrading sulfamethoxazole according to claim 2, characterized in that, In step a2: the weight of the copper foam substrate immersed in each liter of the soaking reaction solution is 180-240g; the amount of 1,3-bis(diphenylphosphine)propane-palladium chloride added per liter of the base solution is 5-15g; and the volume ratio of the mixture to the soaking reaction solution is 5-7:2-3.

5. The method for preparing a composite photocatalytic material for degrading sulfamethoxazole according to claim 2, characterized in that, The steps [2] specifically include the following operations: 4,5-Difluorophenyl-1,2-diamine, triphenylphosphine rhodium chloride, and sodium tetraphenylborate were added to ethanol under an argon atmosphere to form conversion solution A. Intermediate A was immersed in conversion solution A and heated to 50-75°C under a continuous argon atmosphere for 20-28 hours. After cooling to room temperature, the mixture was washed with deionized water and dried at room temperature for 6-10 hours to obtain copper foam with cross-linked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)] on its surface, denoted as intermediate B.

6. The method for preparing a composite photocatalytic material for degrading sulfamethoxazole according to claim 5, characterized in that: The amount of 4,5-difluorophenyl-1,2-diamine, 5-10g of triphenylphosphine rhodium chloride, and 20-40g of sodium tetraphenylborate added per liter of the conversion solution A; the weight of intermediate A impregnated in each liter of the conversion solution A is 130-190g.

7. The method for preparing a composite photocatalytic material for degrading sulfamethoxazole according to claim 5, characterized in that, The specific steps [3] include the following operations: c1. Bismuth trioxide, molybdenum trioxide, nitric acid with a mass fraction of 68% and disodium dihydrogen pyrophosphate are added to deionized water and mixed to form a reaction solution. The intermediate B is immersed in the reaction solution and heated in a water bath to 50-70°C for 5-7 hours to assemble Bi2O9Mo2 precursor on the surface of cross-linked poly[(2,5-diaminodifluorophenyl-4-carbonylthiophene)-(2,5-diamidothiophene)] on the surface of copper foam. After taking out the composite copper foam product, it is dried for 6-8 hours and recorded as intermediate C. c2. Add neodymium nitrate and ammonium molybdate to deionized water to form conversion solution B. Immerse the intermediate C in the conversion solution B, heat to 150-180℃, react for 3-5 hours, cool to room temperature, and dry the product for 6-8 hours to convert the Bi2O9Mo2 precursor into BiNdO9Mo2 nanocrystals, and finally obtain the composite photocatalytic material.

8. The method for preparing a composite photocatalytic material for degrading sulfamethoxazole according to claim 7, characterized in that: In step c1, the concentration of nitric acid in the reaction solution is 0.5-1 mol / L, and the amount of bismuth trioxide added per liter of the reaction solution is 80-100 g, the amount of molybdenum trioxide added is 140-180 g, and the amount of disodium dihydrogen pyrophosphate added is 15-40 g; the amount of intermediate B immersed in per liter of the reaction solution is 180-200 g.

9. The method for preparing a composite photocatalytic material for degrading sulfamethoxazole according to claim 7, characterized in that: In step c2, the amount of neodymium nitrate added per liter of the conversion solution B is 60-110g and the amount of ammonium molybdate added is 160-190g; the weight of intermediate C immersed in per liter of the conversion solution B is 120-160g.

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