Preparation method of foamed aluminum matrix composite for degrading sewage containing acid red g

Abstract

The application provides a preparation method of a foamed aluminum-based composite material for degrading acid red G-containing sewage, and comprises the following steps: step [1], loading poly-gaumine oxime-based aniline on the surface of a foamed aluminum matrix; step [2], converting the poly-gaumine oxime-based aniline on the surface of the foamed aluminum matrix into a [Sm(PAOAn)2(gly)2] coordination polymer; and step [3], loading BiO9SmMo2 nanocrystals on the surface of the Sm(PAOAn)2(gly)2 coordination polymer. The foamed aluminum-based composite material prepared by the method has outstanding visible light catalytic properties and high performance of visible light catalytic synergistic activation of peroxyacetic acid for degrading acid red G-containing sewage.

Description

Technical Field

[0001] The invention relates to the technical field of acid red G wastewater treatment, in particular to a method for preparing a foamed aluminum-based composite material for degrading acid red G-containing wastewater through photocatalytic synergistic activation of peracetic acid. Background Art

[0002] Acid Red G is an azo compound with two nitrogen atoms forming an azo bond (-N=N-) and a sulfonic acid group. The azo structure of Acid Red G gives it vibrant colors and excellent color fastness, while the sulfonic acid group imparts water solubility and stability in various acidic and alkaline chemical environments. Therefore, Acid Red G is widely used as an azo dye in industries such as dyeing, printing, and textiles. During the production processes using Acid Red G in these industries, a significant proportion of Acid Red G is discharged into the aquatic environment, generating large amounts of wastewater containing Acid Red G. Acid Red G is somewhat soluble and chemically stable, making it difficult to degrade naturally or biodegrade and prone to migration. Upon reaching humans and animals through drinking wastewater containing Acid Red G or through the food chain, Acid Red G is converted into carcinogenic aromatic amines, posing a serious threat to humans and the natural environment.

[0003] After full activation, peracetic acid can generate acetoxy radical CH3C(O)O·, peroxyacetyl radical CH3C(O)OO·, peroxyalkyl radical OOCH3·, OH· hydroxyl radical and singlet oxygen 1 O2 and other strong oxidizing substances, which can break the azo bond of acid red G and destroy the naphthalene ring structure of acid red G, thereby achieving effective degradation of wastewater containing acid red G.

[0004] Therefore, there is an urgent need to develop a material with outstanding visible light catalytic properties and visible light catalytic efficient synergistic activation of peracetic acid for degrading acidic red G wastewater. Summary of the Invention

[0005] In order to overcome the shortcomings of the existing technology, the present invention provides a method for preparing a foamed aluminum-based composite material for degrading acidic red G-containing wastewater. The foamed aluminum-based composite material prepared by this method has outstanding visible light catalytic properties and has the performance of efficiently catalyzing visible light to synergistically activate peracetic acid to degrade acidic red G-containing wastewater.

[0006] The technical solution adopted by the present invention to solve its technical problem is:

[0007] The present invention provides a method for preparing a foamed aluminum-based composite material for degrading wastewater containing acidic red G, comprising the following steps:

[0008] Step [1]: loading polyamidoaniline on the surface of the foamed aluminum substrate;

[0009] Step [2] converting the polyamidoaniline on the surface of the aluminum foam substrate into a [Sm(PAOAn)2(gly)2] coordination polymer;

[0010] Step [3] Loading BiO9SmMo2 nanocrystals on the surface of Sm(PAOAn)2(gly)2 coordination polymer.

[0011] Preferably, the step [1] specifically includes the following operations:

[0012] a1. Phenylacetic acid, urea, ammonium bicarbonate, and ammonium persulfate were added to deionized water and mixed to form a reaction solution; an aluminum foam sample was immersed in the reaction solution and reacted at room temperature for 10-14 hours. The sample was removed and rinsed with deionized water to obtain an aluminum foam with polyaniline loaded on the surface, which was designated as intermediate A.

[0013] a2. Add cyanoacetic acid, hydroxylamine, and ammonium nitrite to deionized water and mix to form a synthetic solution; immerse the intermediate A in the synthetic solution and react at room temperature for 8-10 hours. After removing the sample, rinse it with deionized water and dry it at 30-40°C for 4-6 hours to obtain an aluminum foam loaded with polyamidoaniline on its surface, which is designated as intermediate B.

[0014] Preferably, in step a1, the amount of phenylacetic acid added per liter of the reaction solution is 80-150 g, the amount of urea added is 40-70 g, the amount of ammonium bicarbonate added is 50-80 g, and the amount of ammonium persulfate added is 10-20 g; and the weight of the foamed aluminum immersed in each liter of the reaction solution is 20-40 g.

[0015] Preferably, in step a2, the amount of cyanoacetic acid added to each liter of the synthesis liquid is 40-70 g, the amount of hydroxylamine added is 20-50 g, and the amount of ammonium nitrite added is 10-20 g; and the weight of the intermediate A immersed in each liter of the synthesis liquid is 60-110 g.

[0016] Preferably, the step [2] specifically includes the following operations:

[0017] b1. Glycine, samarium nitrate and sodium periodate were added to deionized water, mixed to form a solution, heated to 70-110 ° C, reacted for 3-5 hours, filtered to obtain a solid product, and the solid product was dried at 40-60 ° C for 3-4 hours to obtain a solid precursor;

[0018] b2. Add aniline, aminoacetic acid, samarium nitrate, sodium perborate, and the solid-phase precursor to deionized water and mix to form a preparation solution; immerse the intermediate B in the preparation solution, heat it in a water bath to 40-60°C, react for 8-10 hours, remove the sample, rinse it with deionized water, and dry it at room temperature for 10-14 hours to obtain foamed aluminum with a surface loaded with [Sm(PAOAn)2(gly)2] coordination polymer, which is recorded as intermediate C.

[0019] Preferably, in step b1, the amount of glycine added to each liter of the generated liquid is 100-140 g, the amount of samarium nitrate added is 40-70 g, and the amount of sodium periodate added is 5-15 g.

[0020] Preferably, in step b2, the amount of aniline added per liter of the preparation solution is 40-60 ml, the amount of aminoacetic acid added is 30-60 g, the amount of samarium nitrate added is 20-40 g, the amount of sodium perborate added is 5-15 g, and the amount of solid-phase precursor added is 80-120 g; the weight of the intermediate B immersed in each liter of the preparation solution is 90-120 g.

[0021] Preferably, the step [3] specifically includes the following operations:

[0022] c1. Add bismuth telluride and samarium chloride to ethanol and mix to form an organic liquid; add molybdic acid and 68% concentrated nitric acid by mass to deionized water and mix to form an inorganic liquid; mix the organic liquid and the inorganic liquid in a certain proportion to form a crystallization liquid.

[0023] c2. Immerse the intermediate C in the crystallization solution and react at room temperature for 24-30 hours. After removing the sample, rinse with deionized water and dry at 50-60°C for 3-6 hours to complete the loading of BiO9SmMo2 nanocrystals on the surface of the [Sm(PAOAn)2(gly)2] coordination polymer, and finally obtain the foam aluminum-based composite material.

[0024] Preferably, in step c1, the amount of bismuth telluride added to each liter of the organic liquid is 40-60 g, and the amount of samarium chloride added is 30-50 g; the amount of molybdic acid added to each liter of the inorganic liquid is 15-40 g, and the mass fraction of nitric acid in the inorganic liquid is 4-8%; the volume ratio between the organic liquid and the inorganic liquid in the crystallization liquid is 3-5:6-9.

[0025] Preferably, in step c2, the weight of the intermediate C immersed in each liter of the crystallization solution is 120-140 g.

[0026] The positive effects of the present invention are as follows: the foam aluminum-based composite material prepared according to the method of the present invention is first formed on the surface of the foam aluminum matrix on the basis of polyamidoaniline (PAOAn) organic matter, the nitrogen atom of the NH2 group of the polyamidoaniline (PAOAn) organic matter provides lone pairs of electrons to share with samarium ions, and the O atom of the aminoacetate (gly) and the nitrogen atom of the NH2 group are shared with the samarium ions to form a connected structure of [Sm(PAOAn)2(gly)2] coordination polymer, and then BiO9SmMo2 alloy nanoparticles are loaded on the surface of the [Sm(PAOAn)2(gly)2] coordination polymer. Among them, the nitrogen atom of the NH2 group of the amidoxime group of the [Sm(PAOAn)2(gly)2] coordination polymer and the O atom and NH2 group nitrogen atom of the aminoacetate (gly) group have a strong adsorption effect on acid red G under the conditions of the reaction with samarium ions, and the polyamidoaniline (PAOAn) organic matter has good light absorption performance in the visible light region; at the same time, the BiO9SmMo2 crystal is an orthorhombic system with a space group of Pnma (62). The BiO9SmMo2 alloy nanoparticles have a strong adsorption effect on acid red G under the conditions of the reaction with samarium ions. The orbital hybridization of Mo and oxygen has a narrow band gap and good visible light reactivity. In addition, the interface between the [Sm(PAOAn)2(gly)2] coordination polymer and BiO9SmMo2 alloy nanoparticles can enhance the generation of visible light photogenerated electrons and holes, thereby reducing the activation energy of peracetic acid, thereby promoting the generation of CH3C(O)OO·, CH3C(O)O· and ·OH free radicals, which are used to break the azo bond of acid red G and destroy the naphthalene ring structure of acid red G, thereby achieving the effective degradation of acid red G-containing wastewater.

[0027] In summary, the foamed aluminum-based composite material prepared according to the present invention has outstanding visible light catalytic properties and has the performance of efficiently catalyzing visible light to synergistically activate peracetic acid to degrade acidic red G-containing wastewater. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 This is a schematic diagram of the preparation process of the foamed aluminum-based composite material of the present invention;

[0029] Figure 2 Schematic diagram of the microstructure of the foamed aluminum-based composite material of the present invention;

[0030] Figure 3 is the relative concentration of residual acid red G in the simulated acid red G-containing wastewater treated under different conditions in Example 1 of the present invention;

[0031] Figure 4 is the relative concentration of residual acid red G in the simulated acid red G-containing wastewater treated under different conditions in Comparative Example 1 of the present invention;

[0032] Figure 5It is the relative concentration of residual acid red G in the simulated acid red G-containing wastewater treated under different conditions in Comparative Example 2 of the present invention. DETAILED DESCRIPTION

[0033] Reference Figure 1 The present invention provides a method for preparing a foamed aluminum-based composite material for degrading acidic red G-containing wastewater, comprising the following steps:

[0034] Step [1]: loading polyamidoaniline on the surface of the aluminum foam substrate, specifically comprising the following operations:

[0035] a1. Phenylacetic acid, urea, ammonium bicarbonate, and ammonium persulfate were added to deionized water and mixed to form a reaction solution, wherein the amount of phenylacetic acid added per liter of the reaction solution was 80-150 g, the amount of urea added was 40-70 g, the amount of ammonium bicarbonate added was 50-80 g, and the amount of ammonium persulfate added was 10-20 g. An aluminum foam sample was immersed in the reaction solution (the weight of the aluminum foam immersed per liter of the reaction solution was 20-40 g), and the reaction was carried out at room temperature for 10-14 hours. The sample was removed and rinsed with deionized water to obtain an aluminum foam loaded with polyaniline, which was recorded as intermediate A.

[0036] a2. Add cyanoacetic acid, hydroxylamine, and ammonium nitrite to deionized water and mix to form a synthetic solution, wherein the amount of cyanoacetic acid added to each liter of the synthetic solution is 40-70 g, the amount of hydroxylamine added is 20-50 g, and the amount of ammonium nitrite added is 10-20 g; the intermediate A is immersed in the synthetic solution (the weight of the intermediate A immersed in each liter of the synthetic solution is 60-110 g), and the reaction is carried out at room temperature for 8-10 hours. After removing the sample, it is washed with deionized water and dried at 30-40°C for 4-6 hours to obtain a foamed aluminum with polyamidoaniline on the surface, which is recorded as intermediate B; wherein the structural formula of the polyamidoaniline (PAOAn) is:

[0037]

[0038] Step [2] converts the polyamidoaniline on the surface of the aluminum foam substrate into a [Sm(PAOAn)2(gly)2] coordination polymer, specifically comprising the following operations:

[0039] b1. Glycine, samarium nitrate and sodium periodate are added to deionized water and mixed to form a resulting solution (the amount of glycine added per liter of the resulting solution is 100-140 g, the amount of samarium nitrate added is 40-70 g, and the amount of sodium periodate added is 5-15 g), heated to 70-110 ° C, reacted for 3-5 hours, filtered to obtain a solid product, and the solid product is dried at 40-60 ° C for 3-4 hours to obtain a solid precursor;

[0040] b2. Aniline, aminoacetic acid, samarium nitrate, sodium perborate and the solid-phase precursor were added to deionized water and mixed to form a preparation solution, wherein the amount of aniline added per liter of the preparation solution was 40-60 ml, the amount of aminoacetic acid added was 30-60 g, the amount of samarium nitrate added was 20-40 g, the amount of sodium perborate added was 5-15 g, and the amount of solid-phase precursor added was 80-120 g; the intermediate B was immersed in the preparation solution (the weight of the intermediate B immersed in each liter of the preparation solution was 90-120 g), heated to 40-60 ° C in a water bath, reacted for 8-10 hours, and the sample was removed and washed with deionized water and dried at room temperature for 10-14 hours to obtain a foamed aluminum having a surface loaded with [Sm(PAOAn)2(gly)2] coordination polymer, recorded as intermediate C; wherein the structural formula of the [Sm(PAOAn)2(gly)2] coordination polymer is:

[0041]

[0042] Step [3] loading BiO9SmMo2 nanocrystals on the surface of the Sm(PAOAn)2(gly)2 coordination polymer, specifically comprising the following operations:

[0043] c1. Bismuth telluride and samarium chloride are added to ethanol and mixed to form an organic liquid (bismuth telluride is added in an amount of 40 to 60 g and samarium chloride is added in an amount of 30 to 50 g per liter of the organic liquid); molybdic acid and 68% concentrated nitric acid are added to deionized water and mixed to form an inorganic liquid (molybdic acid is added in an amount of 15 to 40 g per liter of the inorganic liquid and the mass fraction of nitric acid in the inorganic liquid is 4 to 8%); the organic liquid and the inorganic liquid are mixed in a volume ratio of 3 to 5:6 to 9 to form a crystallization liquid,

[0044] c2. The intermediate C was immersed in the crystallization solution (the weight of the intermediate C immersed in each liter of the crystallization solution was 120-140 g), and the reaction was carried out at room temperature for 24-30 hours. After removing the sample, it was washed with deionized water and dried at 50-60°C for 3-6 hours to complete the loading of BiO9SmMo2 nanocrystals on the surface of the [Sm(PAOAn)2(gly)2] coordination polymer. Finally, the foamed aluminum-based composite material (foamed aluminum [Sm(PAOAn)2(gly)2] coordination polymer / BiO9SmMo2 alloy nanocrystals) was obtained. The microstructure diagram is shown in FIG. Figure 2 shown.

[0045] The preferred embodiments of the present invention are described below with examples.

[0046] Example 1

[0047] Preferred embodiment 1 of the present invention provides a method for preparing a foamed aluminum-based composite material for degrading acidic red G-containing wastewater, comprising the following steps:

[0048] Step [1]: loading polyamidoaniline on the surface of the aluminum foam substrate, specifically comprising the following operations:

[0049] a1. Phenylacetic acid, urea, ammonium bicarbonate, and ammonium persulfate were added to deionized water and mixed to form a reaction solution. The amount of phenylacetic acid added was 120 g, the amount of urea added was 60 g, the amount of ammonium bicarbonate added was 70 g, and the amount of ammonium persulfate added was 18 g per liter of the reaction solution. An aluminum foam sample was immersed in the reaction solution (the weight of the aluminum foam immersed in the reaction solution was 35 g per liter of the reaction solution). The reaction was carried out at room temperature for 13 hours. The sample was removed and rinsed with deionized water to obtain an aluminum foam with polyaniline loaded on its surface, which was recorded as intermediate A.

[0050] a2. Add cyanoacetic acid, hydroxylamine, and ammonium nitrite to deionized water and mix to form a synthetic solution, wherein the amount of cyanoacetic acid added per liter of the synthetic solution is 60 g, the amount of hydroxylamine added is 40 g, and the amount of ammonium nitrite added is 15 g; the intermediate A is immersed in the synthetic solution (the weight of the intermediate A immersed in the synthetic solution is 90 g per liter of the synthetic solution), and the reaction is carried out at room temperature for 9 hours. After removing the sample, it is rinsed with deionized water and dried at 40°C for 5 hours to obtain an aluminum foam loaded with polyamidoaniline on its surface, which is recorded as intermediate B.

[0051] Step [2] converts the polyamidoaniline on the surface of the aluminum foam substrate into a [Sm(PAOAn)2(gly)2] coordination polymer, specifically comprising the following operations:

[0052] b1. Glycine, samarium nitrate and sodium periodate were added to deionized water and mixed to form a resulting solution (130 g of glycine was added per liter of the resulting solution, 60 g of samarium nitrate and 10 g of sodium periodate), heated to 80 ° C, reacted for 4 hours, filtered to obtain a solid product, and the solid product was dried at 50 ° C for 4 hours to obtain a solid precursor;

[0053] b2. Add aniline, aminoacetic acid, samarium nitrate, sodium perborate and the solid-phase precursor to deionized water and mix to form a preparation solution, wherein the amount of aniline added per liter of the preparation solution is 50 ml, the amount of aminoacetic acid added is 50 g, the amount of samarium nitrate added is 30 g, the amount of sodium perborate added is 10 g, and the amount of solid-phase precursor added is 110 g; immerse the intermediate B in the preparation solution (the weight of the intermediate B immersed in each liter of the preparation solution is 100 g), heat to 55°C in a water bath, react for 9 hours, remove the sample, rinse with deionized water, and dry at room temperature for 12 hours to obtain foamed aluminum with a surface loaded with [Sm(PAOAn)2(gly)2] coordination polymer, which is recorded as intermediate C.

[0054] Step [3] loading BiO9SmMo2 nanocrystals on the surface of the Sm(PAOAn)2(gly)2 coordination polymer, specifically comprising the following operations:

[0055] c1. Bismuth telluride and samarium chloride were added to ethanol and mixed to form an organic solution (50 g of bismuth telluride and 45 g of samarium chloride were added per liter of the organic solution); molybdic acid and 68% concentrated nitric acid were added to deionized water and mixed to form an inorganic solution (30 g of molybdic acid were added per liter of the inorganic solution, and the mass fraction of nitric acid in the inorganic solution was 6%); the organic solution and the inorganic solution were mixed in a volume ratio of 5:7 to form a crystallization solution.

[0056] c2. The intermediate C was immersed in the crystallization solution (the weight of the intermediate C immersed in each liter of the crystallization solution was 130 g), and the reaction was carried out at room temperature for 26 hours. After removing the sample, it was rinsed with deionized water and dried at 54°C for 5 hours to complete the loading of BiO9SmMo2 nanocrystals on the surface of the [Sm(PAOAn)2(gly)2] coordination polymer, and finally the foam aluminum-based composite material (foam aluminum [Sm(PAOAn)2(gly)2] coordination polymer / BiO9SmMo2 alloy nanocrystals) was obtained, which is recorded as Example 1.

[0057] Comparative Example 1

[0058] This comparative example 1 provides a method for preparing a foamed aluminum-based composite material for degrading acidic red G-containing wastewater, comprising the following steps:

[0059] Step [1]: loading polyamidoaniline on the surface of the aluminum foam substrate, specifically comprising the following operations:

[0060] a1. Phenylacetic acid, urea, ammonium bicarbonate, and ammonium persulfate were added to deionized water and mixed to form a reaction solution. The amount of phenylacetic acid added was 90 g, the amount of urea added was 60 g, the amount of ammonium bicarbonate added was 60 g, and the amount of ammonium persulfate added was 12 g per liter of the reaction solution. An aluminum foam sample was immersed in the reaction solution (the weight of the aluminum foam immersed in the reaction solution was 25 g per liter of the reaction solution). The reaction was carried out at room temperature for 11 hours. The sample was removed and rinsed with deionized water to obtain an aluminum foam with polyaniline loaded on its surface, which was recorded as intermediate A.

[0061] a2. Add cyanoacetic acid, hydroxylamine, and ammonium nitrite to deionized water and mix to form a synthetic solution, wherein the amount of cyanoacetic acid added per liter of the synthetic solution is 50 g, the amount of hydroxylamine added is 30 g, and the amount of ammonium nitrite added is 15 g; the intermediate A is immersed in the synthetic solution (the weight of the intermediate A immersed in the synthetic solution is 70 g per liter of the synthetic solution), and the reaction is carried out at room temperature for 9 hours. After removing the sample, it is rinsed with deionized water and dried at 35°C for 5 hours to obtain an aluminum foam loaded with polyamidoaniline on the surface, which is recorded as intermediate B.

[0062] Step [2] converts the polyamidoaniline on the surface of the aluminum foam substrate into a [Sm(PAOAn)2(gly)2] coordination polymer, specifically comprising the following operations:

[0063] b1. Glycine, samarium nitrate and sodium periodate were added to deionized water and mixed to form a resulting solution (the amount of glycine added per liter of the resulting solution was 120 g, 50 g of samarium nitrate and 7 g of sodium periodate), heated to 75 ° C, reacted for 4 hours, filtered to obtain a solid product, and the solid product was dried at 50 ° C for 3 hours to obtain a solid precursor;

[0064] b2. Add aniline, aminoacetic acid, samarium nitrate, sodium perborate and the solid-phase precursor to deionized water and mix to form a preparation solution, wherein the amount of aniline added per liter of the preparation solution is 45 ml, the amount of aminoacetic acid added is 40 g, the amount of samarium nitrate added is 25 g, the amount of sodium perborate added is 7 g, and the amount of solid-phase precursor added is 100 g; immerse the intermediate B in the preparation solution (the weight of the intermediate B immersed in each liter of the preparation solution is 100 g), heat to 50°C in a water bath, react for 9 hours, remove the sample, rinse with deionized water, and dry at room temperature for 12 hours to obtain foamed aluminum with a surface loaded with [Sm(PAOAn)2(gly)2] coordination polymer, which is recorded as Comparative Example 1.

[0065] Comparative Example 2

[0066] This comparative example 2 provides a method for preparing a foamed aluminum-based composite material for degrading acidic red G-containing wastewater, comprising the following steps:

[0067] Step [1]: loading polyamidoaniline on the surface of the aluminum foam substrate, specifically comprising the following operations:

[0068] a1. Phenylacetic acid, urea, ammonium bicarbonate, and ammonium persulfate were added to deionized water and mixed to form a reaction solution. The amount of phenylacetic acid added was 110 g, the amount of urea added was 60 g, the amount of ammonium bicarbonate added was 70 g, and the amount of ammonium persulfate added was 14 g per liter of the reaction solution. An aluminum foam sample was immersed in the reaction solution (the weight of the aluminum foam immersed in the reaction solution was 24 g per liter of the reaction solution). The reaction was carried out at room temperature for 12 hours. The sample was removed and rinsed with deionized water to obtain an aluminum foam with polyaniline loaded on its surface, which was recorded as intermediate A.

[0069] a2. Add cyanoacetic acid, hydroxylamine, and ammonium nitrite to deionized water and mix to form a synthetic solution, wherein the amount of cyanoacetic acid added per liter of the synthetic solution is 45 g, the amount of hydroxylamine added is 30 g, and the amount of ammonium nitrite added is 15 g; the intermediate A is immersed in the synthetic solution (the weight of the intermediate A immersed in the synthetic solution is 80 g per liter of the synthetic solution), and the reaction is carried out at room temperature for 9 hours. After removing the sample, it is rinsed with deionized water and dried at 35°C for 5 hours to obtain an aluminum foam loaded with polyamidoaniline on the surface, which is recorded as intermediate B.

[0070] Step [2] loading BiO9SmMo2 nanocrystals on the surface of polyamidoaniline, specifically comprising the following operations:

[0071] c1. Bismuth telluride and samarium chloride were added to ethanol and mixed to form an organic solution (bismuth telluride was added in an amount of 45 g and samarium chloride was added in an amount of 40 g per liter of the organic solution); molybdic acid and 68% concentrated nitric acid were added to deionized water and mixed to form an inorganic solution (molybdic acid was added in an amount of 20 g per liter of the inorganic solution and nitric acid was added in an amount of 5% by mass in the inorganic solution); the organic solution and the inorganic solution were mixed in a volume ratio of 3 to 5:6 to 9 to form a crystallization solution.

[0072] c2. The intermediate B was immersed in the crystallization solution (the weight of the intermediate B immersed in each liter of the crystallization solution was 125 g), and the reaction was carried out at room temperature for 24 hours. After removing the sample, it was rinsed with deionized water and dried at 55°C for 5 hours to complete the loading of BiO9SmMo2 nanocrystals on the surface of polyamidoaniline, and finally the foamed aluminum-based composite material (foamed aluminum polyamidoaniline / BiO9SmMo2 alloy nanocrystals) was obtained, which was recorded as Comparative Example 2.

[0073] In order to analyze the visible light catalytic properties of Example 1, Comparative Example 1 and Comparative Example 2 and the performance of visible light catalytic synergistic activation of peracetic acid in degrading acid red G-containing wastewater, acid red G was added to deionized water to form simulated acid red G-containing wastewater with an acid red G concentration of 50 mg / L. 100 ml of the simulated acid red G-containing wastewater was poured into a beaker, and 20 g of Example 1, Comparative Example 1 and Comparative Example 2 were placed in the beaker respectively. A peracetic acid solution with a mass concentration of 15% was added to the simulated acid red G-containing wastewater to make the peracetic acid added amount 300 μmol / L. A 500W xenon lamp light source was used to irradiate Comparative Example 1, Comparative Example 2 and Example 1 with visible light of a wavelength of 480 nm for 40 minutes. The residual acid red G concentration during the degradation process of the acid red G-containing wastewater was measured using a UV-visible spectrophotometer (control groups with only light and no light were also set up). The results are as follows: Figure 3-5As shown by the figure, the relative residual acid red G concentration of Example 1 in degrading acid red G-containing wastewater under visible light irradiation and synergistic activation of peroxyacetic acid is only 0.06, which is significantly lower than the relative residual acid red G concentration (0.32 and 0.41, respectively) of Comparative Examples 1 and 2 in degrading acid red G-containing wastewater under the same conditions. In addition, even under the condition of only visible light irradiation without the addition of peroxyacetic acid, the relative residual acid red G concentration of Example 1 in degrading acid red G-containing wastewater is only 0.48, which is significantly lower than the relative residual acid red G concentration (0.73 and 0.81, respectively) of Comparative Examples 1 and 2 under the same conditions. Therefore, it can be seen that Example 1 has outstanding photocatalytic properties.

[0074] In summary, the foam aluminum-based composite material prepared according to the present application has outstanding visible light catalytic properties and high performance in degrading acid red G-containing wastewater under visible light catalytic synergistic activation of peroxyacetic acid.

[0075] To further illustrate in detail, three additional examples are provided below.

[0076] Example 2

[0077] The preferred embodiment 2 of the present application provides a preparation method of a foam aluminum-based composite material for degrading acid red G-containing wastewater, comprising the following steps:

[0078] Step [1] loading poly-amidoxime-based aniline on the surface of the foam aluminum matrix, specifically including the following operations:

[0079] a1. adding phenylacetic acid, urea, ammonium bicarbonate, and ammonium persulfate into deionized water to form a reaction solution, wherein the amount of phenylacetic acid added in each liter of the reaction solution is 80 g, the amount of urea added is 70 g, the amount of ammonium bicarbonate added is 50 g, and the amount of ammonium persulfate added is 20 g; immersing a foam aluminum sample into the reaction solution (the weight of the foam aluminum immersed in each liter of the reaction solution is 20 g), and reacting at room temperature for 10 hours; after taking out the sample, washing with deionized water to obtain foam aluminum with poly-aniline loaded on the surface, which is denoted as intermediate A;

[0080] a2. adding cyanoacetic acid, hydroxylamine, and ammonium nitrite into deionized water to form a synthesis solution, wherein the amount of cyanoacetic acid added in each liter of the synthesis solution is 40 g, the amount of hydroxylamine added is 50 g, and the amount of ammonium nitrite added is 20 g; immersing the intermediate A into the synthesis solution (the weight of the intermediate A immersed in each liter of the synthesis solution is 60 g), and reacting at room temperature for 8 hours; after taking out the sample, washing with deionized water, and drying at 30°C for 6 hours, foam aluminum with poly-amidoxime-based aniline loaded on the surface is obtained, which is denoted as intermediate B.

[0081] Step [2] converts the poly-glyoxylate aniline on the surface of the aluminum foam matrix into [Sm(PAOAn)2(gly)2] coordination polymer, which specifically includes the following operations:

[0082] b1. Add aminoacetic acid, samarium nitrate, and sodium periodate into deionized water to form a generating solution (100 g of aminoacetic acid, 70 g of samarium nitrate, and 5 g of sodium periodate are added into the generating solution per liter), heat to 70°C, and react for 5 hours to obtain a solid-phase product. Dry the solid-phase product at 60°C for 3 hours to obtain a solid-phase precursor;

[0083] b2. Add aniline, aminoacetic acid, samarium nitrate, sodium perborate, and the solid-phase precursor into deionized water to form a preparation solution (60 ml of aniline, 30 g of aminoacetic acid, 20 g of samarium nitrate, 5 g of sodium perborate, and 80 g of the solid-phase precursor are added into the preparation solution per liter); immerse the intermediate B in the preparation solution (90 g of the intermediate B is immersed in the preparation solution per liter), heat to 60°C in a water bath, and react for 8 hours. After the sample is taken out, wash with deionized water, and dry at room temperature for 10 hours to obtain aluminum foam loaded with [Sm(PAOAn)2(gly)2] coordination polymer on the surface, which is denoted as intermediate C.

[0084] Step [3] loads BiO9SmMo2 nanocrystals on the surface of the Sm(PAOAn)2(gly)2 coordination polymer, which specifically includes the following operations:

[0085] c1. Add bismuth telluride and samarium chloride into ethanol to form an organic solution (60 g of bismuth telluride and 50 g of samarium chloride are added into the organic solution per liter); add molybdic acid and concentrated nitric acid with a mass fraction of 68% into deionized water to form an inorganic solution (15 g of molybdic acid is added into the inorganic solution per liter, and the mass fraction of nitric acid in the inorganic solution is 4%); mix the organic solution and the inorganic solution in a volume ratio of 5:6 to form a crystallization solution,

[0086] c2. Immerse the intermediate C in the crystallization solution (120 g of the intermediate C is immersed in the crystallization solution per liter), react at room temperature for 24 hours, and then take out the sample, wash with deionized water, and dry at 50°C for 6 hours to complete the loading of BiO9SmMo2 nanocrystals on the surface of the [Sm(PAOAn)2(gly)2] coordination polymer, thereby obtaining the aluminum foam matrix composite (aluminum foam [Sm(PAOAn)2(gly)2] coordination polymer / BiO9SmMo2 alloy nanocrystals).

[0087] Example 3

[0088] Preferred embodiment 3 of the present invention provides a method for preparing a foamed aluminum-based composite material for degrading wastewater containing acidic red G, comprising the following steps:

[0089] Step [1]: loading polyamidoaniline on the surface of the aluminum foam substrate, specifically comprising the following operations:

[0090] a1. Phenylacetic acid, urea, ammonium bicarbonate, and ammonium persulfate were added to deionized water and mixed to form a reaction solution. The amount of phenylacetic acid added was 150 g, the amount of urea added was 40 g, the amount of ammonium bicarbonate added was 80 g, and the amount of ammonium persulfate added was 10 g per liter of the reaction solution. An aluminum foam sample was immersed in the reaction solution (the weight of the aluminum foam immersed in the reaction solution was 40 g per liter of the reaction solution). The reaction was carried out at room temperature for 14 hours. The sample was removed and rinsed with deionized water to obtain an aluminum foam loaded with polyaniline on its surface, which was recorded as intermediate A.

[0091] a2. Add cyanoacetic acid, hydroxylamine, and ammonium nitrite to deionized water and mix to form a synthetic solution, wherein the amount of cyanoacetic acid added per liter of the synthetic solution is 70 g, the amount of hydroxylamine added is 20 g, and the amount of ammonium nitrite added is 10 g; the intermediate A is immersed in the synthetic solution (the weight of the intermediate A immersed in the synthetic solution is 110 g per liter of the synthetic solution), and the reaction is carried out at room temperature for 10 hours. After removing the sample, it is rinsed with deionized water and dried at 40°C for 4 hours to obtain an aluminum foam loaded with polyamidoaniline on its surface, which is recorded as intermediate B.

[0092] Step [2] converts the polyamidoaniline on the surface of the aluminum foam substrate into a [Sm(PAOAn)2(gly)2] coordination polymer, specifically comprising the following operations:

[0093] b1. Glycine, samarium nitrate and sodium periodate were added to deionized water and mixed to form a generated solution (140 g of glycine was added per liter of the generated solution, 40 g of samarium nitrate and 15 g of sodium periodate were added), heated to 110 ° C, reacted for 3 hours, filtered to obtain a solid product, and the solid product was dried at 40 ° C for 4 hours to obtain a solid precursor;

[0094] b2. Add aniline, aminoacetic acid, samarium nitrate, sodium perborate and the solid-phase precursor to deionized water and mix to form a preparation solution, wherein the amount of aniline added per liter of the preparation solution is 40 ml, the amount of aminoacetic acid added is 60 g, the amount of samarium nitrate added is 40 g, the amount of sodium perborate added is 15 g, and the amount of solid-phase precursor added is 120 g; immerse the intermediate B in the preparation solution (the weight of the intermediate B immersed in each liter of the preparation solution is 120 g), heat to 40°C in a water bath, react for 10 hours, remove the sample, rinse with deionized water, and dry at room temperature for 14 hours to obtain foamed aluminum with a surface loaded with [Sm(PAOAn)2(gly)2] coordination polymer, which is recorded as intermediate C.

[0095] Step [3] loading BiO9SmMo2 nanocrystals on the surface of Sm(PAOAn)2(gly)2 coordination polymer, specifically comprising the following operations:

[0096] c1. adding bismuth telluride and samarium chloride into ethanol to form an organic liquid (40 g of bismuth telluride and 30 g of samarium chloride are added into each liter of the organic liquid); adding molybdic acid and 68% concentrated nitric acid into deionized water to form an inorganic liquid (40 g of molybdic acid is added into each liter of the inorganic liquid, and the mass fraction of nitric acid in the inorganic liquid is 8%); mixing the organic liquid and the inorganic liquid in a volume ratio of 3:7 to form a crystallization liquid,

[0097] c2. immersing the intermediate C into the crystallization liquid (140 g of the intermediate C is immersed into each liter of the crystallization liquid), and reacting at room temperature for 30 hours; after taking out the sample, washing with deionized water, and drying at 60°C for 3 hours, the loading of BiO9SmMo2 nanocrystals on the surface of [Sm(PAOAn)2(gly)2] coordination polymer is completed, and finally the foam aluminum-based composite material (foam aluminum [Sm(PAOAn)2(gly)2] coordination polymer / BiO9SmMo2 alloy nanocrystals) is obtained.

[0098] Example 4

[0099] The preferred embodiment 4 of the present application provides a preparation method of a foam aluminum-based composite material for degrading sewage containing acid red G, comprising the following steps:

[0100] Step [1] loading poly-gaumine oxime-based aniline on the surface of a foam aluminum matrix, specifically comprising the following operations:

[0101] a1. adding phenylacetic acid, urea, ammonium bicarbonate, and ammonium persulfate into deionized water to form a reaction liquid, wherein 115 g of phenylacetic acid, 55 g of urea, 65 g of ammonium bicarbonate, and 15 g of ammonium persulfate are added into each liter of the reaction liquid; immersing a foam aluminum sample into the reaction liquid (30 g of the foam aluminum is immersed into each liter of the reaction liquid), and reacting at room temperature for 12 hours; after taking out the sample, washing with deionized water, a foam aluminum with a surface loaded with polyaniline is obtained, which is denoted as intermediate A;

[0102] a2. Add cyanoacetic acid, hydroxylamine, and ammonium nitrite to deionized water and mix to form a synthetic solution, wherein the amount of cyanoacetic acid added per liter of the synthetic solution is 55 g, the amount of hydroxylamine added is 35 g, and the amount of ammonium nitrite added is 15 g; the intermediate A is immersed in the synthetic solution (the weight of the intermediate A immersed in the synthetic solution is 85 g per liter of the synthetic solution) and reacted at room temperature for 9 hours. After removing the sample, it is rinsed with deionized water and dried at 35°C for 5 hours to obtain an aluminum foam loaded with polyamidoaniline on its surface, which is recorded as intermediate B.

[0103] Step [2] converts the polyamidoaniline on the surface of the aluminum foam substrate into a [Sm(PAOAn)2(gly)2] coordination polymer, specifically comprising the following operations:

[0104] b1. Glycine, samarium nitrate and sodium periodate were added to deionized water and mixed to form a resulting solution (120 g of glycine was added per liter of the resulting solution, 55 g of samarium nitrate and 10 g of sodium periodate), heated to 90 ° C, reacted for 4 hours, filtered to obtain a solid product, and the solid product was dried at 50 ° C for 3.5 hours to obtain a solid precursor;

[0105] b2. Add aniline, aminoacetic acid, samarium nitrate, sodium perborate and the solid-phase precursor to deionized water and mix to form a preparation solution, wherein the amount of aniline added per liter of the preparation solution is 50 ml, the amount of aminoacetic acid added is 45 g, the amount of samarium nitrate added is 30 g, the amount of sodium perborate added is 10 g, and the amount of solid-phase precursor added is 100 g; immerse the intermediate B in the preparation solution (the weight of the intermediate B immersed in each liter of the preparation solution is 105 g), heat to 50°C in a water bath, react for 9 hours, remove the sample, rinse with deionized water, and dry at room temperature for 12 hours to obtain foamed aluminum with a surface loaded with [Sm(PAOAn)2(gly)2] coordination polymer, which is recorded as intermediate C.

[0106] Step [3] loading BiO9SmMo2 nanocrystals on the surface of the Sm(PAOAn)2(gly)2 coordination polymer, specifically comprising the following operations:

[0107] c1. Bismuth telluride and samarium chloride were added to ethanol and mixed to form an organic solution (50 g of bismuth telluride and 40 g of samarium chloride were added per liter of the organic solution); molybdic acid and 68% concentrated nitric acid were added to deionized water and mixed to form an inorganic solution (29 g of molybdic acid were added per liter of the inorganic solution, and the mass fraction of nitric acid in the inorganic solution was 6%); the organic solution and the inorganic solution were mixed in a volume ratio of 4:7 to form a crystallization solution.

[0108] c2. The intermediate C is immersed in the crystallization solution (130 g of intermediate C per liter of the crystallization solution), and the reaction is carried out at room temperature for 27 hours. After taking out the sample, the sample is washed with deionized water, and dried at 55°C for 4.5 hours. The loading of BiO9SmMo2 nanocrystals on the surface of the [Sm(PAOAn)2(gly)2] coordination polymer is completed, and finally the foam aluminum-based composite material (foam aluminum [Sm(PAOAn)2(gly)2] coordination polymer / BiO9SmMo2 alloy nanocrystal) is obtained.

[0109] The above merely describes preferred embodiments of the present application, and it should be understood that the above description of the embodiments is only used to help understand the method of the present application and its core idea, and is not used to limit the protection scope of the present application. Any modification, equivalent replacement, etc. within the idea and principles of the present application should be included in the protection scope of the present application.

Claims

1. A method for preparing a foamed aluminum-based composite material for degrading acidic red G-containing wastewater, characterized in that: The following steps are included: Step [1]: Loading polyamidoaniline on the surface of the aluminum foam substrate, specifically comprising the following operations: a1. Phenylacetic acid, urea, ammonium bicarbonate, and ammonium persulfate were added to deionized water and mixed to form a reaction solution; the aluminum foam sample was immersed in the reaction solution and reacted at room temperature for 10-14 hours. The sample was removed and washed with deionized water to obtain an aluminum foam surface loaded with polyaniline, referred to as intermediate A; a2. Cyanoacetic acid, hydroxylamine, and ammonium nitrite were added to deionized water and mixed to form a synthetic solution; the intermediate A was immersed in the synthetic solution and reacted at room temperature for 8-10 hours. The sample was removed and washed with deionized water and dried at 30-40 ° C for 4-6 hours to obtain an aluminum foam with a surface load of polyamidoaniline, referred to as intermediate B; Step [2] converting the polyamidoaniline on the surface of the aluminum foam substrate into a [Sm(PAOAn)2(gly)2] coordination polymer, specifically comprising the following operations: b1. Glycine, samarium nitrate and sodium periodate are added to deionized water, mixed to form a solution, heated to 70-110 ℃, reacted for 3-5 hours, filtered to obtain a solid product, and the solid product is dried at 40-60 ℃ for 3-4 hours to obtain a solid precursor; b2. Aniline, glycine, samarium nitrate, sodium perborate, and the solid-phase precursor were added to deionized water and mixed to form a preparation solution; Intermediate B was immersed in the preparation solution, heated in a water bath to 40-60°C, and reacted for 8-10 hours. The sample was removed, rinsed with deionized water, and dried at room temperature for 10-14 hours to obtain an aluminum foam with a surface-loaded [Sm(PAOAn)2(gly)2] coordination polymer, designated as Intermediate C; Step [3] Loading BiO9SmMo2 nanocrystals on the surface of the Sm(PAOAn)2(gly)2 coordination polymer, specifically comprising the following operations: c1. Bismuth telluride and samarium chloride were added to ethanol and mixed to form an organic liquid; molybdic acid and 68% concentrated nitric acid were added to deionized water and mixed to form an inorganic liquid; the organic liquid and the inorganic liquid were mixed in a certain proportion to form a crystallization liquid; c2. Immerse the intermediate C in the crystallization solution and react at room temperature for 24-30 hours. After removing the sample, rinse with deionized water and dry at 50-60°C for 3-6 hours to complete the loading of BiO9SmMo2 nanocrystals on the surface of the [Sm(PAOAn)2(gly)2] coordination polymer, and finally obtain the foam aluminum-based composite material.

2. The method for preparing a foamed aluminum-based composite material for degrading acidic red G-containing wastewater according to claim 1, characterized in that: In step a1, the amount of phenylacetic acid added per liter of the reaction solution is 80-150 g, the amount of urea added is 40-70 g, the amount of ammonium bicarbonate added is 50-80 g, and the amount of ammonium persulfate added is 10-20 g; and the weight of the aluminum foam immersed in each liter of the reaction solution is 20-40 g.

3. The method for preparing a foamed aluminum-based composite material for degrading acidic red G-containing wastewater according to claim 1, characterized in that: In step a2, the amount of cyanoacetic acid added to each liter of the synthesis liquid is 40-70 g, the amount of hydroxylamine added is 20-50 g, and the amount of ammonium nitrite added is 10-20 g; and the weight of the intermediate A immersed in each liter of the synthesis liquid is 60-110 g.

4. The method for preparing a foamed aluminum-based composite material for degrading acidic red G-containing wastewater according to claim 1, characterized in that: In step b1, the amount of glycine added to each liter of the generated liquid is 100-140 g, the amount of samarium nitrate added is 40-70 g, and the amount of sodium periodate added is 5-15 g.

5. The method for preparing a foamed aluminum-based composite material for degrading acidic red G-containing wastewater according to claim 1, characterized in that: In step b2, the amount of aniline added per liter of the preparation solution is 40-60 ml, the amount of aminoacetic acid added is 30-60 g, the amount of samarium nitrate added is 20-40 g, the amount of sodium perborate added is 5-15 g, and the amount of solid-phase precursor added is 80-120 g; the weight of the intermediate B immersed in each liter of the preparation solution is 90-120 g.

6. The method for preparing a foamed aluminum-based composite material for degrading acidic red G-containing wastewater according to claim 1, characterized in that: In step c1, the amount of bismuth telluride added to each liter of the organic liquid is 40-60 g, and the amount of samarium chloride added is 30-50 g; the amount of molybdic acid added to each liter of the inorganic liquid is 15-40 g, and the mass fraction of nitric acid in the inorganic liquid is 4-8%; and the volume ratio of the organic liquid to the inorganic liquid in the crystallization liquid is 3-5:6-9.

7. The method for preparing a foamed aluminum-based composite material for degrading acidic red G-containing wastewater according to claim 1, characterized in that: In step c2, the weight of the intermediate C immersed in each liter of the crystallization solution is 120-140 g.

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