Preparation method of photocatalytic material for treating alizarin red sewage

Abstract

The invention provides a preparation method of a photocatalytic material for treating alizarin red sewage. The preparation method comprises the following steps: (1) preparing a precursor reactant corresponding to a coordination compound Tm6Se6 (C7H8N2O4) 6; (2) loading a coordination compound Tm6Se6 (C7H8N2O4) 6 on the surface of the foam iron matrix; and (3) converting the coordination compound Tm6Se6 (C7H8N2O4) 6 into the thulium selenium coordination polymer [Tm6Se6 (C7H6N2O2) 6 (C7H4N2O2) 12] n. The photocatalytic material prepared by the method disclosed by the invention has efficient visible light and ultraviolet light photocatalytic degradation rate of alizarin red and excellent repeated use photocatalytic stability.

Description

Technical Field

[0001] The present invention relates to the technical field of alizarin red sewage treatment, and particularly to a preparation method of a photocatalytic material for treating alizarin red sewage. Background Art

[0002] Alizarin red is a water-soluble compound dye with a hydroxy-substituted anthraquinone structure, having excellent stability properties such as bright color, wash resistance, and light fastness. In the chemical fiber and textile industry, alizarin red can be used for dyeing nylon and wool; in the medical field, alizarin red can chelate with calcium salts to form an orange-red complex, which can be used for physiological analysis of bone tissue and bone cells. At the same time, alizarin red can also be used for staining and labeling of cells, proteins, nucleic acids, and other molecules, for studying the morphology, structure, and function of cells, proteins, nucleic acids, and other molecules; in geological research, alizarin red can be used for detecting minerals contained in rock thin sections. Alizarin red has carcinogenic and mutagenic toxicity, and its toxicity is generated by the specific sites of the cell DNA acting with the metabolized diol epoxides and quinones. Alizarin red can change the structures of human serum albumin and bovine serum albumin; can inhibit the actions of human acetylcholinesterase and α-amylase; can intercalate with cell DNA, causing changes in the DNA structure. Alizarin red sewage has serious toxic effects, which can not only migrate and pollute, but also cause direct death of aquatic fish or accumulate in fish bodies. With the economic and social development, the generation and discharge of a large amount of alizarin red sewage pose a serious threat to the human living environment.

[0003] Photocatalytic materials have the property of absorbing light energy to generate photoexcited electrons and photoexcited holes. These photoexcited electrons and photoexcited holes react with water molecules and oxygen in contact with the photocatalytic material / alizarin red sewage interface to generate strongly oxidizing free radicals, and then oxidatively degrade the alizarin red adsorbed on the photocatalytic material / alizarin red sewage interface. However, the current photocatalytic materials for photocatalytic degradation of alizarin red sewage not only have a narrow light absorption wavelength range, but also generate a small number of strongly oxidizing free radicals during the photocatalytic degradation of alizarin red sewage, resulting in a very low photocatalytic degradation efficiency of alizarin red sewage. At the same time, the instability of the repeated use performance of the existing photocatalytic materials has become a bottleneck in the development of industrial photocatalytic degradation technology for alizarin red sewage. Summary of the Invention

[0004] In order to overcome the deficiencies of the prior art, the present invention provides a preparation method of a photocatalytic material for treating alizarin red sewage. The photocatalytic material prepared by this method has a high visible light and ultraviolet light photocatalytic degradation rate of alizarin red and excellent repeated use photocatalytic stability.

[0005] The technical solution adopted by the present invention to solve its technical problems is:

[0006] The present invention provides a preparation method of a photocatalytic material for treating alizarin red sewage, comprising the following steps:

[0007] Step [1] Prepare the coordination compound Tm 6 Se 6 (C 7 H 8 N 2 O 4 ) 6 corresponding precursor reactant;

[0008] Step [2] Load the coordination compound Tm 6 Se 6 (C 7 H 8 N 2 O 4 ) 6 ;

[0009] Step [3] Convert the coordination compound Tm 6 Se 6 (C 7 H 8 N 2 O 4 ) 6 into the thulium selenium coordination polymer [Tm 6 Se 6 (C 7 H 6 N 2 O 2 ) 6 (C 7 H 4 N 2 O 2 ) 12 n .

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

[0011] a1. Add 2,4-dimethylimidazole and acetic acid to deionized water and mix to form a reaction base solution; add acetaldehyde and tert-butyl hydroperoxide to deionized water and mix to form a reaction oxidation solution;

[0012] a2. Heat the reaction base solution in a water bath to 45 - 70 °C, then add a certain amount of the reaction oxidation solution, react for 3 - 6 hours under stirring, cool to room temperature, filter to obtain a solid phase, wash with deionized water, and dry at room temperature for 6 - 8 hours to obtain the precursor reactant.

[0013] Preferably, in step a1, the addition amount of 2,4-dimethylimidazole in each liter of the reaction base solution is 30 - 50 g, and the addition amount of acetic acid is 80 - 140 mL; the addition amount of acetaldehyde in each liter of the reaction oxidation solution is 20 - 60 mL, and the addition amount of tert-butyl hydroperoxide is 5 - 20 mL. ​

[0014] Preferably, in step a2, the volume ratio between the reaction oxidation liquid and the reaction base liquid is 1-2:3-5.

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

[0016] b1. Add thulium nitrate, selenous acid and ferrous sulfate into deionized water, mix to form a generating liquid, heat to 80-100 °C and react for 4-7 hours, cool to room temperature, filter to obtain a solid phase, and dry at room temperature for 4-6 hours to obtain Tm 6 Se 6 ;

[0017] b2. Add the said precursor reactant, Tm 6 Se 6 , 2,4-dimethylimidazole and acetic acid into deionized water, mix to obtain a loading liquid, immerse the iron foam sample into the loading liquid, heat to 110-140 °C and react for 8-12 hours, cool to room temperature, take out the iron foam sample, and dry at room temperature for 5-8 hours to obtain an iron foam with a coordination compound Tm 6 Se 6 (C 7 H 8 N 2 O 4 ) 6 loaded on its surface, denoted as intermediate A.

[0018] Preferably, in step b1, the addition amount of thulium nitrate in each liter of the said generating liquid is 30-80 g, the addition amount of selenous acid is 70-110 g, and the addition amount of ferrous sulfate is 10-20 g.

[0019] Preferably, in step b2, the addition amount of the precursor reactant in each liter of the said loading liquid is 70-100 g, the addition amount of Tm 6 Se 6 is 40-80 g, the addition amount of 2,4-dimethylimidazole is 15-40 g, and the addition amount of acetic acid is 10-30 mL; the weight of the iron foam immersed in each liter of the said loading liquid is 60-80 g.

[0020] Preferably, the said step [3] specifically includes the following operations:

[0021] c1. Add 1H-benzimidazole-4,7-diol, azodiisooctanenitrile and the said precursor reactant into dimethyl sulfoxide, mix to form a synthesis liquid;

[0022] c2. Heat the synthesis liquid in a water bath to 50-65 °C, immerse the intermediate A into the synthesis liquid, react for 36-44 hours, take out the iron foam sample, and dry at room temperature for 6-8 hours to obtain an iron foam with a thulium selenium coordination polymer [Tm 6 Se6 (C 7 H 6 N 2 O 2 ) 6 (C 7 H 4 N 2 O 2 ) 12 n The foam iron is the photocatalytic material as described above.

[0023] Preferably, in step c1, the addition amount of 1H-benzoimidazole-4,7-diol in each liter of the synthesis solution is 60-90 g, the addition amount of azodiisobutyronitrile is 10-20 g, and the addition amount of the precursor reactant is 70-100 g.

[0024] Preferably, in step c2, the weight of intermediate A immersed in each liter of the synthesis solution is 70-110 g.

[0025] The positive effect of the present invention: The photocatalytic material prepared by the method according to the present invention has thulium selenium coordination polymer [Tm 6 Se 6 (C 7 H 6 N 2 O 2 ) 6 (C 7 H 4 N 2 O 2 ) 12 n loaded on the surface of the foam iron, which uses thulium selenium compound Tm 6 Se 6 as the central body of the coordination polymer (where the selenium atom of Tm 6 Se 6 is located at the vertex of the regular octahedron, and the thulium atom is located outside the vertex of the regular octahedron), and uses Tm 6 Se 6 (C 7 H 6 N 2 O 2 ) 6 (C 7 H 4 N 2 O 2 ) 12 as the repeating unit (where six (C 7 H 6 N 2 O 2 )(C 7 H 4 N 2 O​​2 ) 2 The nitrogen atoms provide lone pairs of electrons to coordinate with Tm respectively 6 Se 6 Six Tm ions located outside the six vertices of the octahedron form six coordination bonds, thus constituting the repeating unit), and finally through the coordination polymer central body Tm 6 Se 6 and the organic ligand (C 7 H 6 N 2 O 2 ) 6 (C 7 H 4 N 2 O 2 ) 12 to form a three-dimensional network coordination polymer. Based on the above structural characteristics, the repeating unit Tm 6 Se 6 (C 7 H 6 N 2 O 2 ) 6 (C 7 H 4 N 2 O 2 ) 12 has a strong charge attraction with the carbon-carbon double bond of the alizarin red benzene ring, and can realize the chemical adsorption of alizarin red; in addition, the thulium selenium coordination polymer [Tm 6 Se 6 (C 7 H 6 N 2 O 2 ) 6 (C 7 H 4 N 2 O 2 ) 12 ) n has a narrow band gap. The coordination polymer central body Tm 6 Se 6 and the organic ligand (C 7 H 6 N 2 O 2 ) 6 (C 7 H 4 N 2 O 2 ) 12 can produce charge transfer transitions, which is beneficial to expanding the thulium selenium coordination polymer [Tm 6 Se 6 (C 7 H 6N 2 O 2 ) 6 (C 7 H 4 N 2 O 2 ) 12 n The absorption wavelength range of [substance] can further promote the generation of a large number of highly active ·OH free radicals during the photocatalytic degradation of alizarin red wastewater, effectively causing the cleavage of the fused benzene ring of alizarin red, and ultimately completely degrading alizarin red wastewater.

[0026] In summary, the photocatalytic material prepared according to the present invention has high photocatalytic degradation rates for visible light and ultraviolet light of alizarin red and excellent photocatalytic stability for repeated use. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 is a schematic flow chart of the preparation of the photocatalytic material of the present invention;

[0028] Figure 2 is a schematic diagram of the microscopic structure of the photocatalytic material of the present invention;

[0029] Figure 3 is the relative concentration of residual alizarin red during the photocatalytic degradation of simulated alizarin red-containing wastewater by Example 1, Comparative Example 1, and Comparative Example 2 of the present invention under visible light and ultraviolet light;

[0030] Figure 4 is the relationship between the number of uses and the relative concentration of residual alizarin red when using Example 1, Comparative Example 1, and Comparative Example 2 to treat simulated alizarin red-containing wastewater under visible light;

[0031] Figure 5 is the relationship between the number of uses and the relative concentration of residual alizarin red when using Example 1, Comparative Example 1, and Comparative Example 2 to treat simulated alizarin red-containing wastewater under ultraviolet light.

[0032] Figure 6 is the [substance] of Tm 6 Se 6 molecular structure schematic diagram;

[0033] Figure 7 is the coordination compound Tm 6 Se 6 (C 7 H 8 N 2 O 4 ) 6 structural schematic diagram;

[0034] Figure 8 is the thulium selenium coordination polymer [Tm 6 Se 6 ​(C 7 H 6 N 2 O 2 ) 6 (C 7 H 4 N 2 O 2 ) 12 n Schematic structural diagram of;

[0035] Figure 9 is the schematic structural diagram of the coordination compound Tm(C 7 H 8 N 2 O 4 ) 6 described in Comparative Example 2;

[0036] Figure 10 is the schematic structural diagram of the coordination polymer [Tm(C 7 H 6 N 2 O 2 ) 6 (C 7 H 4 N 2 O 2 ) 12 n described in Comparative Example 2. Specific embodiments

[0037] Referring to Figure 1 , the present invention provides a preparation method of a photocatalytic material for treating alizarin red sewage, comprising the following steps:

[0038] Step [1] Preparation of the coordination compound Tm 6 Se 6 (C 7 H 8 N 2 O 4 ) 6 corresponding precursor reactants, specifically including the following operations:

[0039] a1. Add 2,4-dimethylimidazole and acetic acid to deionized water and mix to form a reaction base solution (the addition amount of 2,4-dimethylimidazole in each liter of the reaction base solution is 30 - 50 g, and the addition amount of acetic acid is 80 - 140 mL); add acetaldehyde and tert-butyl hydroperoxide to deionized water and mix to form a reaction oxidation solution (the addition amount of acetaldehyde in each liter of the reaction oxidation solution is 20 - 60 mL, and the addition amount of tert-butyl hydroperoxide is 5 - 20 mL);

[0040] ​​a2. Heat the reaction base solution in a water bath to 45 - 70 °C, then add a certain amount of reaction oxidation solution (the volume ratio between the reaction oxidation solution and the reaction base solution is 1 - 2:3 - 5), react for 3 - 6 hours under stirring, cool to room temperature, filter to obtain the solid phase, wash with deionized water and dry at room temperature for 6 - 8 hours to obtain the said precursor reactant.

[0041] Among them, the formation reaction formula of the said precursor reactant is:

[0042]

[0043] Step [2] Load the coordination compound Tm 6 Se 6 (C 7 H 8 N 2 O 4 ) 6 on the surface of the iron foam matrix, and the specific operations are as follows:

[0044] b1. Add thulium nitrate, selenous acid and ferrous sulfate to deionized water, mix to form a generation solution (the addition amount of thulium nitrate in each liter of the said generation solution is 30 - 80 g, the addition amount of selenous acid is 70 - 110 g, and the addition amount of ferrous sulfate is 10 - 20 g), heat to 80 - 100 °C and react for 4 - 7 hours, cool to room temperature, filter to obtain the solid phase, and dry at room temperature for 4 - 6 hours to obtain Tm 6 Se 6 (the structure is as Figure 6 ) shown;

[0045] The reaction formula involved in this step is:

[0046] 6Tm(NO 3 ) 3 + 9H 2 SeO 3 + 42FeSO 4 + 21SO 4 2- → 21Fe 2 (SO 4 ) 3 + Tm 6 Se 6 + 18(NO 3 ) 3 - + 3SeO 3 + 18OH -

[0047] b2. Mix the said precursor reactant, Tm 6 Se 6, 2,4-dimethylimidazole and acetic acid are added to deionized water, and a loading solution is obtained (the addition amount of the precursor reactant in each liter of the loading solution is 70-100 g, Tm 6 Se 6 the addition amount is 40-80 g, the addition amount of 2,4-dimethylimidazole is 15-40 g, and the addition amount of acetic acid is 10-30 mL). The iron foam sample is immersed in the loading solution (the weight of the iron foam immersed in each liter of the loading solution is 60-80 g), heated to 110-140 °C and reacted for 8-12 hours, cooled to room temperature, the iron foam sample is taken out, and dried at room temperature for 5-8 hours to obtain iron foam with a coordination compound Tm 6 Se 6 (C 7 H 8 N 2 O 4 ) 6 loaded on the surface, denoted as intermediate A; wherein, the reaction formula involved in this step is:

[0048]

[0049] The structure of the coordination compound Tm 6 Se 6 (C 7 H 8 N 2 O 4 ) 6 is as shown in Figure 7 .

[0050] Step [3] converts the coordination compound Tm 6 Se 6 (C 7 H 8 N 2 O 4 ) 6 into a thulium selenide coordination polymer [Tm 6 Se 6 (C 7 H 6 N 2 O 2 ) 6 (C 7 H 4 N 2 O 2 ) 12 n , specifically including the following operations:

[0051] ​c1. Add 1H - benzimidazole - 4,7 - diol, azodiisobutyronitrile, and the said precursor reactant into dimethyl sulfoxide, and mix them to form a synthesis solution. The addition amount of 1H - benzimidazole - 4,7 - diol in each liter of the synthesis solution is 60 - 90 g, the addition amount of azodiisobutyronitrile is 10 - 20 g, and the addition amount of the precursor reactant is 70 - 100 g;

[0052] c2. Heat the synthesis solution in a water bath to 50 - 65 °C, immerse intermediate A into the synthesis solution (the weight of intermediate A immersed in each liter of the synthesis solution is 70 - 110 g), react for 36 - 44 hours, take out the foam iron sample, and dry it at room temperature for 6 - 8 hours to obtain foam iron with thulium selenium coordination polymer [Tm 6 Se 6 (C 7 H 6 N 2 O 2 ) 6 (C 7 H 4 N 2 O 2 ) 12 n on its surface, which is the said photocatalytic material (the schematic diagram of its microstructure is as shown in Figure 2 ), and the structure of the thulium selenium coordination polymer [Tm 6 Se 6 (C 7 H 6 N 2 O 2 ) 6 (C 7 H 4 N 2 O 2 ) 12 n is as shown in Figure 8 .

[0053] The preferred embodiments of the present invention will be illustrated by way of example below.

[0054] Example 1

[0055] The preferred embodiment 1 of the present invention provides a preparation method of a photocatalytic material for treating alizarin red sewage, which comprises the following steps:

[0056] Step [1] Prepare the corresponding precursor reactant of the coordination compound Tm 6 Se 6 (C 7 H 8 N 2 O 4 ) 6 , and the specific operations are as follows: ​​

[0057] a1. Add 2,4-dimethylimidazole and acetic acid to deionized water and mix to form a reaction base solution (the addition amount of 2,4-dimethylimidazole in each liter of the reaction base solution is 40 g, and the addition amount of acetic acid is 120 mL); add acetaldehyde and tert-butyl hydroperoxide to deionized water and mix to form a reaction oxidation solution (the addition amount of acetaldehyde in each liter of the reaction oxidation solution is 30 mL, and the addition amount of tert-butyl hydroperoxide is 15 mL).

[0058] a2. Heat the reaction base solution in a water bath to 65 °C, then add a certain amount of the reaction oxidation solution (the volume ratio between the reaction oxidation solution and the reaction base solution is 2:5), react for 5 hours under stirring, cool to room temperature, filter to obtain a solid phase, wash with deionized water, and dry at room temperature for 7 hours to obtain the precursor reactant.

[0059] Step [2]: Load the coordination compound Tm 6 Se 6 (C 7 H 8 N 2 O 4 ) 6 on the surface of the iron foam matrix, and the specific operations are as follows:

[0060] b1. Add thulium nitrate, selenous acid, and ferrous sulfate to deionized water and mix to form a generating solution (the addition amount of thulium nitrate in each liter of the generating solution is 50 g, the addition amount of selenous acid is 100 g, and the addition amount of ferrous sulfate is 15 g), heat to 90 °C and react for 6 hours, cool to room temperature, filter to obtain a solid phase, and dry at room temperature for 5 hours to obtain Tm 6 Se 6 ;

[0061] b2. Add the precursor reactant, Tm 6 Se 6 , 2,4-dimethylimidazole, and acetic acid to deionized water and mix to obtain a loading solution (the addition amount of the precursor reactant in each liter of the loading solution is 90 g, the addition amount of Tm 6 Se 6 is 70 g, the addition amount of 2,4-dimethylimidazole is 30 g, and the addition amount of acetic acid is 20 mL). Immerse the iron foam sample in the loading solution (the weight of the iron foam immersed in each liter of the loading solution is 70 g), heat to 130 °C and react for 9 hours, cool to room temperature, take out the iron foam sample, and dry at room temperature for 7 hours to obtain the iron foam with the coordination compound Tm 6 Se 6 (C 7 H 8 N 2 O 4 ) 6 loaded on its surface, denoted as intermediate A.

[0062] Step [3] converts the coordination compound Tm 6 Se 6 (C 7 H 8 N 2 O 4 ) 6 into the thulium selenium coordination polymer [Tm 6 Se 6 (C 7 H 6 N 2 O 2 ) 6 (C 7 H 4 N 2 O 2 ) 12 n , specifically including the following operations:

[0063] c1. Add 1H-benzoimidazole-4,7-diol, azodiisooctanenitrile, and the said precursor reactant into dimethyl sulfoxide, and mix to form a synthesis solution. The addition amount of 1H-benzoimidazole-4,7-diol in each liter of the synthesis solution is 80 g, the addition amount of azodiisooctanenitrile is 15 g, and the addition amount of the precursor reactant is 80 g;

[0064] c2. Heat the synthesis solution in a water bath to 60 °C, immerse the intermediate A into the synthesis solution (the weight of the intermediate A immersed in each liter of the synthesis solution is 90 g), react for 38 hours, take out the iron foam sample, and dry it at room temperature for 6 hours to obtain the iron foam with the thulium selenium coordination polymer [Tm 6 Se 6 (C 7 H 6 N 2 O 2 ) 6 (C 7 H 4 N 2 O 2 ) 12 n loaded on its surface, which is the said photocatalytic material, denoted as Example 1.

[0065] Comparative Example 1

[0066] This Comparative Example 1 provides a preparation method of a photocatalytic material for treating alizarin red sewage, including the following steps:

[0067] Step [1] Prepare the coordination compound Tm 6 Se 6 (C 7 H 8 N 2 O​​4 ) 6 The corresponding precursor reactant, specifically including the following operations:

[0068] a1. Add 2,4-dimethylimidazole and acetic acid to deionized water and mix to form a reaction base solution (the addition amount of 2,4-dimethylimidazole in each liter of the reaction base solution is 40 g, and the addition amount of acetic acid is 90 mL); add acetaldehyde and tert-butyl hydroperoxide to deionized water and mix to form a reaction oxidation solution (the addition amount of acetaldehyde in each liter of the reaction oxidation solution is 30 mL, and the addition amount of tert-butyl hydroperoxide is 8 mL);

[0069] a2. Heat the reaction base solution in a water bath to 50 °C, then add a certain amount of the reaction oxidation solution (the volume ratio between the reaction oxidation solution and the reaction base solution is 2:3), react for 4 hours under stirring, cool to room temperature, filter to obtain a solid phase, wash with deionized water, and dry at room temperature for 7 hours to obtain the precursor reactant.

[0070] Step [2] Load the coordination compound Tm 6 Se 6 (C 7 H 8 N 2 O 4 ) 6 , specifically including the following operations:

[0071] b1. Add thulium nitrate, selenous acid, and ferrous sulfate to deionized water and mix to form a generating solution (the addition amount of thulium nitrate in each liter of the generating solution is 40 g, the addition amount of selenous acid is 90 g, and the addition amount of ferrous sulfate is 12 g), heat to 90 °C and react for 5 hours, cool to room temperature, filter to obtain a solid phase, and dry at room temperature for 5 hours to obtain Tm 6 Se 6 ;

[0072] b2. Add the precursor reactant, Tm 6 Se 6 , 2,4-dimethylimidazole, and acetic acid to deionized water and mix to obtain a loading solution (the addition amount of the precursor reactant in each liter of the loading solution is 80 g, the addition amount of Tm 6 Se 6 is 70 g, the addition amount of 2,4-dimethylimidazole is 20 g, and the addition amount of acetic acid is 14 mL), immerse the foam iron sample in the loading solution (the weight of the foam iron immersed in each liter of the loading solution is 65 g), heat to 120 °C and react for 10 hours, cool to room temperature, take out the foam iron sample, and dry at room temperature for 6 hours to obtain the foam iron with the coordination compound Tm 6 Se 6 (C 7 H 8 N 2O 4 ) 6 The foamed iron is denoted as Comparative Example 1.

[0073] Comparative Example 2

[0074] This Comparative Example 2 provides a preparation method of a photocatalytic material for treating alizarin red sewage, which comprises the following steps:

[0075] Step [1] Prepare a coordination compound Tm(C 7 H 8 N 2 O 4 ) 6 The corresponding precursor reactant, specifically including the following operations:

[0076] a1. Add 2,4-dimethylimidazole and acetic acid to deionized water and mix to form a reaction base solution (the addition amount of 2,4-dimethylimidazole in each liter of the reaction base solution is 35 g, and the addition amount of acetic acid is 100 mL); add acetaldehyde and tert-butyl hydroperoxide to deionized water and mix to form a reaction oxidation solution (the addition amount of acetaldehyde in each liter of the reaction oxidation solution is 40 mL, and the addition amount of tert-butyl hydroperoxide is 10 mL);

[0077] a2. Heat the reaction base solution in a water bath to 60 °C, then add a certain amount of the reaction oxidation solution (the volume ratio between the reaction oxidation solution and the reaction base solution is 1:3), react for 4 hours under stirring, cool to room temperature, filter to obtain a solid phase, wash with deionized water and dry at room temperature for 7 hours to obtain the precursor reactant.

[0078] Step [2] Load the coordination compound Tm 6 Se 6 (C 7 H 8 N 2 O 4 ) 6 , specifically including the following operations:

[0079] b1. Add the precursor reactant, thulium nitrate, 2,4-dimethylimidazole, and acetic acid to deionized water and mix to obtain a loading solution (the addition amount of the precursor reactant in each liter of the loading solution is 90 g, the addition amount of thulium nitrate is 60 g, the addition amount of 2,4-dimethylimidazole is 20 g, and the addition amount of acetic acid is 15 mL), immerse the foamed iron sample in the loading solution (the weight of the foamed iron immersed in each liter of the loading solution is 70 g), heat to 120 °C and react for 10 hours, cool to room temperature, take out the foamed iron sample, and dry at room temperature for 6 hours to obtain the surface loaded with the coordination compound Tm(C 7 H 8 N 2 O 4 ) 6The iron foam is denoted as intermediate A; the chemical reaction equation involved in this step is:

[0080]

[0081] The molecular structure of the coordination compound Tm(C 7 H 8 N 2 O 4 ) 6 is as shown in Figure 9 Figure.

[0082] In step [3], the coordination compound Tm(C 7 H 8 N 2 O 4 ) 6 is converted into the thulium coordination polymer [Tm(C 7 H 6 N 2 O 2 ) 6 (C 7 H 4 N 2 O 2 ) 12 n , and the specific operations are as follows:

[0083] c1. Add 1H-benzoimidazole-4,7-diol, azodiisobutyronitrile, and the above-mentioned precursor reactant into dimethyl sulfoxide to form a synthesis solution. The addition amount of 1H-benzoimidazole-4,7-diol in each liter of the synthesis solution is 70 g, the addition amount of azodiisobutyronitrile is 15 g, and the addition amount of the precursor reactant is 90 g;

[0084] c2. Heat the synthesis solution in a water bath to 55 °C, immerse intermediate A in the synthesis solution (the weight of intermediate A immersed in each liter of the synthesis solution is 80 g), react for 40 hours, take out the iron foam sample, and dry it at room temperature for 7 hours to obtain the iron foam with the thulium coordination polymer [Tm(C 7 H 6 N 2 O 2 ) 6 (C 7 H 4 N 2 O 2 ) 12 n loaded on its surface, which is the photocatalytic material denoted as Comparative Example 2. Among them, the thulium coordination polymer [Tm(C 7 H 6 N 2 O 2 ) 6 (C​​7 H 4 N 2 O 2 ) 12 n The structure of Figure 10 is shown as follows.

[0085] In order to analyze the degradation rate of alizarin red sewage by photocatalysis in Example 1, Comparative Example 1 and Comparative Example 2 and the photocatalytic stability of their recycling use, alizarin red was added to deionized water to form simulated alizarin red sewage with an alizarin red concentration of 20 mg / L. 1000 ml of the simulated alizarin red sewage was respectively poured into beakers, and 10 g of Example 1, Comparative Example 1 and Comparative Example 2 were respectively put into the beakers. The simulated alizarin red sewage was irradiated and degraded with a 300 W xenon lamp light source under visible light with a wavelength of 520 nm and ultraviolet light with a wavelength of 280 nm for 100 minutes. The relative concentrations of the residual alizarin red in the simulated sewage after 100 minutes of photocatalytic degradation are as Figure 3 shown. It can be seen from the figure that the relative concentrations of the residual alizarin red in Example 1 for photocatalytic degradation of the simulated sewage under simulated visible light and ultraviolet light irradiation conditions are only 0.1 and 0.08 respectively, while under the same conditions, the relative concentrations of the residual alizarin red in Comparative Example 1 are as high as 0.79 and 0.75 respectively, and the relative concentrations of the residual alizarin red in Comparative Example 2 are 0.57 and 0.55.

[0086] Under the above-mentioned simulated visible light irradiation and ultraviolet light irradiation conditions, Example 1, Comparative Example 1 and Comparative Example 2 were recycled to treat the simulated alizarin red sewage (each time of photocatalytic degradation by irradiation for 100 minutes). The relationships between the number of uses and the relative concentrations of the residual alizarin red are respectively as Figure 4 and Figure 5 shown. It can be seen from the figure that under visible light and ultraviolet light irradiation conditions, when Example 1 was recycled for the 4th time, the relative concentrations of the residual alizarin red in the photocatalytic degradation of the simulated alizarin red sewage with a concentration of 20 mg / L were only 0.17 and 0.12 respectively, which were significantly lower than the relative concentrations of the residual alizarin red when Comparative Example 1 and Comparative Example 2 were recycled for the 4th time (0.95 and 0.93, 0.77 and 0.73 respectively). Obviously, Example 1 has the characteristics of stable and efficient recyclability.

[0087] In summary, the photocatalytic material prepared according to the present invention has a high photocatalytic degradation rate of alizarin red under visible light and ultraviolet light and excellent photocatalytic stability for repeated use.

[0088] For further detailed illustration by way of example, three other examples are provided below.

[0089] Example 2

[0090] A preparation method of a photocatalytic material for treating alizarin red sewage provided by a preferred embodiment 2 of the present invention includes the following steps: ​

[0091] Step [1] Preparation of coordination compound Tm 6 Se 6 (C 7 H 8 N 2 O 4 ) 6 The corresponding precursor reactant, specifically including the following operations:

[0092] a1. Add 2,4-dimethylimidazole and acetic acid to deionized water, and mix to form a reaction base solution (the addition amount of 2,4-dimethylimidazole in each liter of the reaction base solution is 30 g, and the addition amount of acetic acid is 80 mL); add acetaldehyde and tert-butyl hydroperoxide to deionized water, and mix to form a reaction oxidation solution (the addition amount of acetaldehyde in each liter of the reaction oxidation solution is 20 mL, and the addition amount of tert-butyl hydroperoxide is 5 mL);

[0093] a2. Heat the reaction base solution in a water bath to 45 °C, then add a certain amount of the reaction oxidation solution (the volume ratio between the reaction oxidation solution and the reaction base solution is 1:3), react for 6 hours under stirring, cool to room temperature, filter to obtain a solid phase, wash with deionized water and dry at room temperature for 6 hours to obtain the precursor reactant.

[0094] Step [2] Loading of coordination compound Tm 6 Se 6 (C 7 H 8 N 2 O 4 ) 6 , specifically including the following operations:

[0095] b1. Add thulium nitrate, selenious acid and ferrous sulfate to deionized water, and mix to form a generating solution (the addition amount of thulium nitrate in each liter of the generating solution is 30 g, the addition amount of selenious acid is 70 g, and the addition amount of ferrous sulfate is 20 g), heat to 80 °C and react for 7 hours, cool to room temperature, filter to obtain a solid phase, and dry at room temperature for 6 hours to obtain Tm 6 Se 6 ;

[0096] b2. Add the precursor reactant, Tm 6 Se 6 , 2,4-dimethylimidazole and acetic acid to deionized water, and mix to obtain a loading solution (the addition amount of the precursor reactant in each liter of the loading solution is 70 g, Tm 6 Se 6The addition amount is 40 g, the addition amount of 2,4-dimethylimidazole is 40 g, and the addition amount of acetic acid is 10 mL. Immerse the iron foam sample in the loading solution (the weight of the iron foam immersed in each liter of the loading solution is 60 g), heat it to 110 °C and react for 12 hours, cool it to room temperature, take out the iron foam sample, and dry it at room temperature for 8 hours to obtain iron foam with a coordination compound Tm loaded on its surface. 6 Se 6 (C 7 H 8 N 2 O 4 ) 6 on the surface, denoted as intermediate A.

[0097] Step [3] Convert the coordination compound Tm 6 Se 6 (C 7 H 8 N 2 O 4 ) 6 into a thulium selenium coordination polymer [Tm 6 Se 6 (C 7 H 6 N 2 O 2 ) 6 (C 7 H 4 N 2 O 2 ) 12 n , which specifically includes the following operations:

[0098] c1. Add 1H-benzoimidazole-4,7-diol, 2,2'-azobis(2-methylbutyronitrile), and the above-mentioned precursor reactant into dimethyl sulfoxide, and mix them to form a synthesis solution. The addition amount of 1H-benzoimidazole-4,7-diol in each liter of the synthesis solution is 60 g, the addition amount of 2,2'-azobis(2-methylbutyronitrile) is 20 g, and the addition amount of the precursor reactant is 70 g;

[0099] c2. Heat the synthesis solution in a water bath to 50 °C, immerse intermediate A in the synthesis solution (the weight of intermediate A immersed in each liter of the synthesis solution is 70 g), react for 36 hours, take out the iron foam sample, and dry it at room temperature for 6 hours to obtain iron foam with a thulium selenium coordination polymer [Tm 6 Se 6 (C 7 H 6 N 2 O 2 ) 6 (C 7 H 4 N 2 O 2 )​12 n The iron foam is the photocatalytic material mentioned above.

[0100] Example 3

[0101] The preferred Example 3 of the present invention provides a preparation method of a photocatalytic material for treating alizarin red sewage, which comprises the following steps:

[0102] Step [1] Prepare the coordination compound Tm 6 Se 6 (C 7 H 8 N 2 O 4 ) 6 The corresponding precursor reactants, which specifically include the following operations:

[0103] a1. Add 2,4-dimethylimidazole and acetic acid to deionized water to form a reaction base solution (the addition amount of 2,4-dimethylimidazole in each liter of the reaction base solution is 50 g, and the addition amount of acetic acid is 140 mL); add acetaldehyde and tert-butyl hydroperoxide to deionized water to form a reaction oxidation solution (the addition amount of acetaldehyde in each liter of the reaction oxidation solution is 60 mL, and the addition amount of tert-butyl hydroperoxide is 20 mL);

[0104] a2. Heat the reaction base solution in a water bath to 70 °C, then add a certain amount of the reaction oxidation solution (the volume ratio between the reaction oxidation solution and the reaction base solution is 2:5), react for 3 hours under stirring, cool to room temperature, filter to obtain a solid phase, wash with deionized water, and dry at room temperature for 8 hours to obtain the precursor reactants.

[0105] Step [2] Load the coordination compound Tm 6 Se 6 (C 7 H 8 N 2 O 4 ) 6 on the surface of the iron foam matrix, which specifically includes the following operations:

[0106] b1. Add thulium nitrate, selenous acid and ferrous sulfate to deionized water to form a generating solution (the addition amount of thulium nitrate in each liter of the generating solution is 80 g, the addition amount of selenous acid is 110 g, and the addition amount of ferrous sulfate is 10 g), heat to 100 °C and react for 4 hours, cool to room temperature, filter to obtain a solid phase, and dry at room temperature for 4 hours to obtain Tm 6 Se 6 ;

[0107] b2. Mix the precursor reactants and Tm 6 Se 6 ​, 2,4-dimethylimidazole and acetic acid are added to deionized water, and a loading solution is obtained (the addition amount of the precursor reactant in each liter of the loading solution is 100 g, Tm 6 Se 6 the addition amount is 80 g, the addition amount of 2,4-dimethylimidazole is 15 g, and the addition amount of acetic acid is 30 mL). The iron foam sample is immersed in the loading solution (the weight of the iron foam immersed in each liter of the loading solution is 80 g), heated to 140 °C and reacted for 8 hours, cooled to room temperature, the iron foam sample is taken out, and dried at room temperature for 5 hours to obtain iron foam with a coordination compound Tm 6 Se 6 (C 7 H 8 N 2 O 4 ) 6 loaded on its surface, denoted as intermediate A.

[0108] Step [3] Convert the coordination compound Tm 6 Se 6 (C 7 H 8 N 2 O 4 ) 6 into a thulium selenium coordination polymer [Tm 6 Se 6 (C 7 H 6 N 2 O 2 ) 6 (C 7 H 4 N 2 O 2 ) 12 n , which specifically includes the following operations:

[0109] c1. 1H-benzimidazole-4,7-diol, azodiisooctanenitrile, and the precursor reactant are added to dimethyl sulfoxide to form a synthesis solution, where the addition amount of 1H-benzimidazole-4,7-diol in each liter of the synthesis solution is 90 g, the addition amount of azodiisooctanenitrile is 10 g, and the addition amount of the precursor reactant is 100 g;

[0110] c2. The synthesis solution is heated in a water bath to 65 °C, and the intermediate A is immersed in the synthesis solution (the weight of the intermediate A immersed in each liter of the synthesis solution is 110 g), reacted for 44 hours, the iron foam sample is taken out, and dried at room temperature for 8 hours to obtain iron foam with a thulium selenium coordination polymer [Tm 6 Se 6 (C 7 H 6 N 2 O​2 ) 6 (C 7 H 4 N 2 O 2 ) 12 n The foam iron of 2

[0111] Example 4

[0112] A preferred embodiment 4 of the present invention provides a preparation method of a photocatalytic material for treating alizarin red sewage, comprising the following steps:

[0113] Step [1] Prepare the coordination compound Tm 6 Se 6 (C 7 H 8 N 2 O 4 ) 6 The corresponding precursor reactants, specifically including the following operations:

[0114] a1. Add 2,4-dimethylimidazole and acetic acid to deionized water to form a reaction base solution (the addition amount of 2,4-dimethylimidazole in each liter of the reaction base solution is 40 g, and the addition amount of acetic acid is 110 mL); add acetaldehyde and tert-butyl hydroperoxide to deionized water to form a reaction oxidation solution (the addition amount of acetaldehyde in each liter of the reaction oxidation solution is 40 mL, and the addition amount of tert-butyl hydroperoxide is 12 mL);

[0115] a2. Heat the reaction base solution in a water bath to 55 °C, then add a certain amount of the reaction oxidation solution (the volume ratio between the reaction oxidation solution and the reaction base solution is 2:3), react for 5 hours under stirring, cool to room temperature, filter to obtain a solid phase, wash with deionized water, and dry at room temperature for 7 hours to obtain the precursor reactants.

[0116] Step [2] Load the coordination compound Tm 6 Se 6 (C 7 H 8 N 2 O 4 ) 6 , specifically including the following operations:

[0117] b1. Add thulium nitrate, selenious acid, and ferrous sulfate to deionized water to form a generating solution (the addition amount of thulium nitrate in each liter of the generating solution is 55 g, the addition amount of selenious acid is 90 g, and the addition amount of ferrous sulfate is 15 g), heat to 90 °C and react for 6 hours, cool to room temperature, filter to obtain a solid phase, and dry at room temperature for 5 hours to obtain Tm 6 Se 6 ;​

[0118] b2. Add the precursor reactant, Tm 6 Se 6 , 2,4-dimethylimidazole, and acetic acid to deionized water, and mix to obtain a loading solution (the addition amount of the precursor reactant in each liter of the loading solution is 85 g, the addition amount of Tm 6 Se 6 is 60 g, the addition amount of 2,4-dimethylimidazole is 30 g, and the addition amount of acetic acid is 20 mL). Immerse the iron foam sample in the loading solution (the weight of the iron foam immersed in each liter of the loading solution is 70 g), heat to 125 °C and react for 10 hours, cool to room temperature, take out the iron foam sample, and dry it at room temperature for 6 hours to obtain iron foam with a coordination compound Tm 6 Se 6 (C 7 H 8 N 2 O 4 ) 6 loaded on its surface, denoted as intermediate A.

[0119] Step [3] Convert the coordination compound Tm 6 Se 6 (C 7 H 8 N 2 O 4 ) 6 into a thulium selenium coordination polymer [Tm 6 Se 6 (C 7 H 6 N 2 O 2 ) 6 (C 7 H 4 N 2 O 2 ) 12 n , specifically including the following operations:

[0120] c1. Add 1H-benzimidazole-4,7-diol, azodiisooctanenitrile, and the precursor reactant to dimethyl sulfoxide, and mix to form a synthesis solution, where the addition amount of 1H-benzimidazole-4,7-diol in each liter of the synthesis solution is 75 g, the addition amount of azodiisooctanenitrile is 15 g, and the addition amount of the precursor reactant is 85 g;

[0121] c2. Heat the synthesis solution in a water bath to 60 °C, immerse intermediate A in the synthesis solution (the weight of intermediate A immersed in each liter of the synthesis solution is 90 g), react for 40 hours, take out the iron foam sample, and dry it at room temperature for 7 hours to obtain iron foam with a thulium selenium coordination polymer [Tm 6 Se​6 (C 7 H 6 N 2 O 2 ) 6 (C 7 H 4 N 2 O 2 ) 12 n The foamed iron of

[0122] The above are only the preferred embodiments of the present invention. It should be understood that the description of the above embodiments is only used to help understand the method and its core idea of the present invention, and is not used to limit the protection scope of the present invention. Any modifications, equivalent replacements, etc. made within the thought and principle of the present invention shall be included within the protection scope of the present invention.​

Claims

1. A method for preparing a photocatalytic material for treating alizarin red wastewater, characterized in that: The following steps are included: Step [1] preparing a precursor reactant corresponding to the coordination compound Tm6Se6(C7H8N2O4)6; Step [2] Loading the coordination compound Tm6Se6(C7H8N2O4)6 on the surface of the foamed iron matrix; Step [3] converting the coordination compound Tm6Se6(C7H8N2O4)6 into a thulium selenium coordination polymer [Tm6Se6(C7H6N2O2)6(C7H4N2O2) 12 ] n .

2. The method for preparing a photocatalytic material for treating alizarin red wastewater according to claim 1, characterized in that: The step [1] specifically includes the following operations: a1. Add 2,4-dimethylimidazole and acetic acid to deionized water and mix to form a reaction base liquid; add acetaldehyde and tert-butyl hydrogen peroxide to deionized water and mix to form a reaction oxidation liquid; a2. Heat the reaction base liquid to 45-70°C in a water bath, then add a certain amount of reaction oxidizing liquid, react for 3-6 hours under stirring, cool to room temperature, filter the solid phase, wash with deionized water and dry at room temperature for 6-8 hours to obtain the precursor reactant.

3. The method for preparing a photocatalytic material for treating alizarin red wastewater according to claim 2, characterized in that: In step a1, the amount of 2,4-dimethylimidazole added to each liter of reaction base liquid is 30-50 g, and the amount of acetic acid added is 80-140 mL; the amount of acetaldehyde added to each liter of reaction oxidation liquid is 20-60 mL, and the amount of tert-butyl hydroperoxide added is 5-20 mL.

4. The method for preparing a photocatalytic material for treating alizarin red wastewater according to claim 2, characterized in that: In step a2, the volume ratio between the reaction oxidation liquid and the reaction base liquid is 1-2:3-5.

5. The method for preparing a photocatalytic material for treating alizarin red wastewater according to claim 1, characterized in that: The step [2] specifically includes the following operations: b1. Thulium nitrate, selenious acid and ferrous sulfate were added to deionized water, mixed to form a solution, heated to 80-100 ° C for 4-7 hours, cooled to room temperature, filtered to obtain a solid phase, and dried at room temperature for 4-6 hours to obtain Tm6Se6; b2. Add the precursor reactant, Tm6Se6, 2,4-dimethylimidazole and acetic acid into deionized water, mix to obtain a loading liquid, immerse the foamed iron sample in the loading liquid, heat to 110-140°C for reaction for 8-12 hours, cool to room temperature, take out the foamed iron sample, dry at room temperature for 5-8 hours, and obtain foamed iron with the coordination compound Tm6Se6(C7H8N2O4)6 loaded on the surface, recorded as intermediate A.

6. The method for preparing a photocatalytic material for treating Alizarin Red wastewater according to claim 5, characterized in that: In step b1, the amount of thulium nitrate added to each liter of the generated solution is 30-80 g, the amount of selenious acid added is 70-110 g, and the amount of ferrous sulfate added is 10-20 g.

7. The method for preparing a photocatalytic material for treating Alizarin Red wastewater according to claim 5, characterized in that: In step b2, the amount of precursor reactant added to each liter of the load liquid is 70-100 g, the amount of Tm6Se6 added is 40-80 g, the amount of 2,4-dimethylimidazole added is 15-40 g, and the amount of acetic acid added is 10-30 mL; the weight of the foamed iron immersed in each liter of the load liquid is 60-80 g.

8. The method for preparing a photocatalytic material for treating Alizarin Red wastewater according to claim 1, characterized in that: The step [3] specifically includes the following operations: c1. Add 1H-benzimidazole-4,7-diol, azobisisoheptanonitrile and the precursor to dimethyl sulfoxide and mix to form a synthetic solution; c2. Heat the synthetic solution in a water bath to 50-65°C, immerse the intermediate A in the synthetic solution, react for 36-44 hours, take out the foamed iron sample, dry it at room temperature for 6-8 hours, and obtain a surface-loaded thulium selenium coordination polymer [Tm6Se6(C7H6N2O2)6(C7H4N2O2) 12 ] n The foamed iron is the photocatalytic material.

9. The method for preparing a photocatalytic material for treating Alizarin Red wastewater according to claim 8, characterized in that: In step c1, per liter of the synthesis liquid, the amount of 1H-benzimidazole-4,7-diol added is 60-90 g, the amount of azobisisoheptanenitrile added is 10-20 g, and the amount of the precursor reactant added is 70-100 g.

10. The method for preparing a photocatalytic material for treating Alizarin Red wastewater according to claim 8, characterized in that: In step c2, the weight of the intermediate A immersed in each liter of the synthetic liquid is 70-110 g.

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