Preparation method of composite material for ozone photocatalytic synergistic treatment of unsymmetrical dimethylhydrazine wastewater

Abstract

The present invention provides a preparation method of a composite material for ozone-photocatalytic synergistic treatment of unsymmetrical dimethylhydrazine wastewater, comprising the following steps: step [1] loading a five-4-acetamidobenzotriazole manganese organic substance on the surface of a foamed iron substrate; step [2] converting the five-4-acetamidobenzotriazole manganese on the surface of the foamed iron substrate into five-5-nitro-4-acetamidobenzotriazole manganese through a substitution reaction; step [3] loading Ba2Cu2Gd3Mn2O on the surface of the five-5-nitro-4-acetamidobenzotriazole manganese 12 The composite material prepared by the method of the present invention has the performance of wide spectral response and high efficiency in photocatalytic synergistic ozone oxidation degradation of unsymmetrical dimethylhydrazine wastewater.

Description

Technical Field

[0001] The invention relates to the technical field of unsymmetrical dimethylhydrazine wastewater treatment, in particular to a method for preparing a composite material for ozone-photocatalytic coordinated treatment of unsymmetrical dimethylhydrazine wastewater. Background Art

[0002] Unsymmetrical dimethylhydrazine (UDMH), a liquid propellant, is a high-performance fuel for missiles, satellites, spacecraft, and rockets. With the development of my country's military, defense, and aerospace technologies, the production, storage, and launch processes of UDMH generate significant amounts of wastewater containing it. UDMH is a Class III toxic substance that directly damages the nervous, digestive, and respiratory systems of humans and animals. UDMH can inhibit decarboxylase activity, alter amino acid metabolism, and reduce the inhibitory capacity of gamma-aminobutyric acid. UDMH wastewater is carcinogenic and difficult to degrade naturally, posing a significant threat to human health and society.

[0003] Ozone is a strong oxidizing agent and can directly oxidize the amino group (NH2) of UDMH, thereby degrading it. However, this process is slow and incomplete degradation is difficult. Alternatively, ozone can degrade UDMH by generating ·OH radicals, which can capture oxygen atoms from UDMH. However, the amount of ·OH radicals produced by ozone is insufficient to achieve efficient and complete degradation.

[0004] Photocatalytic materials absorb light energy to generate large amounts of OH radicals, effectively synergizing with ozone to degrade UDMH-containing wastewater. However, currently, there are still no treatment materials and preparation methods with broad spectral response and high treatment efficiency in the field of UDMH wastewater treatment. Summary of the Invention

[0005] In order to overcome the shortcomings of the existing technology, the present invention provides a method for preparing a composite material for ozone photocatalytic synergistic treatment of unsymmetrical dimethylhydrazine wastewater. The composite material prepared by this method has the performance of wide spectral response and high efficiency photocatalytic synergistic ozone oxidation degradation of unsymmetrical dimethylhydrazine 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 composite material for ozone photocatalytic synergistic treatment of unsymmetrical dimethylhydrazine wastewater, comprising the following steps:

[0008] Step [1] loading penta-4-acetamidobenzotriazole manganese [Mn(4-CH3CONH-BTA)5] organic matter on the surface of the foamed iron matrix;

[0009] Step [2] converting the manganese pentadienyl 4-acetamidobenzotriazole [Mn(4-CH3CONH-BTA)5] on the surface of the foamed iron substrate into manganese pentadienyl 5-nitro-4-acetamidobenzotriazole [Mn(5-NO2-4-CH3CONH-BTA)5] through a substitution reaction;

[0010] Step [3] Ba2Cu2Gd3Mn2O is loaded on the surface of penta-5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5] 12 crystal.

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

[0012] a1. Benzotriazole, acetic acid and n-propylamine were added to deionized water and mixed to form a base liquid; tert-butyl peroxybenzoate was added to ethanol and mixed to form an additive liquid; the base liquid and the additive liquid were mixed in a certain proportion to form a synthetic liquid, heated in a water bath to 50-80 ℃, reacted for 8-10 hours, the solid phase product was filtered, and dried in an incubator at 40-50 ℃ for 5-7 hours to obtain 4-acetamidobenzotriazole;

[0013] a2. Add 4-acetamidobenzotriazole and manganese nitrate to deionized water and mix to form an impregnation solution; add a ferric chloride sample to deionized water and mix to form a ferric chloride solution; immerse the foamed iron in the impregnation solution for 15-30 minutes, then add a certain amount of ferric chloride solution and continue immersing for 2-4 hours. Remove the foamed iron sample and dry it at room temperature for 48-72 hours to obtain a foamed iron with penta-4-acetamidobenzotriazole manganese [Mn(4-CH3CONH-BTA)5] loaded on its surface, which is recorded as intermediate A.

[0014] Preferably, in step a1, the amount of benzotriazole added to each liter of the base liquid is 10-30 g, the amount of acetic acid added is 50-80 mL, and the amount of n-propylamine added is 60-90 mL; the amount of tert-butyl perbenzoate added to each liter of the additive liquid is 30-90 mL; and the volume ratio between the base liquid and the additive liquid in the synthetic liquid is 5-9:1-2.

[0015] Preferably, in step a2, the amount of 4-acetamidobenzotriazole added to each liter of the impregnation solution is 50-80 g, and the amount of manganese nitrate added is 30-50 g; the concentration of the ferric chloride solution is 20-40 g / L; the weight of the foamed iron immersed in each liter of the impregnation solution is 70-110 g; and the volume ratio between the ferric chloride solution and the impregnation solution is 1-3:5-7.

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

[0017] b1. A nitric acid concentration of 68% was added to deionized water to form a nitric acid solution; ethyl nitrate was added to ethanol and mixed to form an ethyl nitrate solution; the nitric acid solution was added to the ethyl nitrate solution in a certain proportion and mixed to form a nitro-substituted solution;

[0018] b2. The intermediate A is immersed in the nitro substitution solution and reacted at a water bath temperature of 20-30°C for 0.5-1.5 hours to convert penta-4-acetamidobenzotriazole manganese [Mn(4-CH3CONH-BTA)5] into penta-5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5] through the substitution reaction. The foamed iron sample is taken out and dried at room temperature for 6-10 hours to obtain foamed iron with penta-5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5] loaded on the surface, which is recorded as intermediate B.

[0019] Preferably, in step b1, the mass concentration of the nitric acid solution is 7-12%; the concentration of the ethyl nitrate solution is 15-40 mL / L; and the volume ratio of the nitric acid solution to the ethyl nitrate solution in the nitro-substitute solution is 3-5:1-2.

[0020] Preferably, in step b2, the weight of the intermediate A immersed in each liter of the nitro substitution solution is 160-180 g.

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

[0022] c1. Add barium chloride, copper chloride, gadolinium nitrate, potassium permanganate and ammonium bisulfate to deionized water and mix to form a crystallization solution;

[0023] c2. The intermediate B was immersed in the crystallization solution, heated to 60-90 ° C, reacted for 6-8 hours, washed with deionized water several times, and dried at room temperature for 12-16 hours to complete Ba2Cu2Gd3Mn2O 12 The crystals are loaded on the surface of penta-5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5] to finally obtain the composite material.

[0024] Preferably, in step c1, the barium chloride concentration in the crystallization solution is 30-50 g / L, the copper chloride concentration is 40-90 g / L, the gadolinium nitrate concentration is 100-140 g / L, the potassium permanganate concentration is 40-70 g / L, and the ammonium bisulfate concentration is 20-30 g / L.

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

[0026] The positive effects of the present invention are as follows: the composite material prepared by the method according to the present invention is based on the formation of five 4-acetamidobenzotriazole manganese [Mn(4-CH3CONH-BTA)5] organic matter by using 4-acetamidobenzotriazole as an organic ligand and manganese atom in a foam iron matrix, and the five 4-acetamidobenzotriazole manganese [Mn(4-CH3CONH-BTA)5] organic matter is replaced by five 5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5] organic matter, and Ba2Cu2Gd3Mn2O is loaded on the surface of the five 5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5] organic matter. 12 Crystal, of which: Ba2Cu2Gd3Mn2O 12 The crystal is a tetragonal system with a space group of I4 / mmm(139); the structure of the organic complex of penta-5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5] is a trigonal bipyramid, with the manganese atom located at the center of the trigonal bipyramid and the five organic ligands (5-nitro-4-acetamidobenzotriazole) located at the five vertices of the trigonal bipyramid. Based on the above structural characteristics, the 5-nitro-4-acetamidobenzotriazole in the organic complex of penta-5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5] has a nitrogen-containing heterocyclic structure. The nitrogen-nitrogen double bond of the nitrogen-containing heterocyclic structure allows the benzotriazole to be replaced and modified by nitro and acetamide groups, has a strong electron-withdrawing ability, and can promote OH - Reaction with ozone to form OH radicals; Ba2Cu2Gd3Mn2O 12 The chemical bonding between Gd and O in the crystal makes Ba2Cu2Gd3Mn2O 12 The crystal is prone to form manganese vacancy defects, which are easy to generate photogenerated electrons and holes; Ba2Cu2Gd3Mn2O 12 The interface between the crystal and the organic complex of manganese pentyl 5-nitro-4-acetamidobenzotriazole [Mn(5-NO2-4-CH3CONH-BTA)5] is the active oxidation degradation site of UDMH, which promotes the process of photocatalytic synergistic ozone oxidation degradation of UDMH.

[0027] In summary, the composite material prepared according to the present invention has the performance of wide spectral response and high efficiency in photocatalytic synergistic ozone oxidation degradation of unsymmetrical dimethylhydrazine wastewater. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 1 is a schematic diagram of the preparation process of the composite material of the present invention;

[0029] Figure 2Schematic diagram of the microstructure of the composite material of the present invention;

[0030] Figure 3 The relative concentration of residual unsymmetrical dimethylhydrazine in the simulated unsymmetrical dimethylhydrazine-containing wastewater treated with a concentration of 10 mg / L in Example 1, Comparative Example 1, and Comparative Example 2 of the present invention;

[0031] Figure 4 The relative concentration of residual UDMH in the simulated UDMH-containing wastewater treated in Example 1, Comparative Example 1 and Comparative Example 2 of the present invention at a concentration of 5 mg / L was measured. DETAILED DESCRIPTION

[0032] Reference Figure 1 The present invention provides a method for preparing a composite material for ozone photocatalytic synergistic treatment of unsymmetrical dimethylhydrazine wastewater, comprising the following steps:

[0033] Step [1] loading penta-4-acetamidobenzotriazole manganese [Mn(4-CH3CONH-BTA)5] organic matter on the surface of the foamed iron matrix specifically includes the following operations:

[0034] a1. Benzotriazole, acetic acid and n-propylamine were added to deionized water and mixed to form a base liquid, wherein the amount of benzotriazole added per liter of the base liquid was 10 to 30 g, acetic acid was added in an amount of 50 to 80 mL, and n-propylamine was added in an amount of 60 to 90 mL; tert-butyl perbenzoate was added to ethanol and mixed to form an additive solution, wherein the amount of tert-butyl perbenzoate added per liter of the additive solution was 30 to 90 mL; the base liquid and the additive solution were mixed in a ratio of 5 to 9:1 to 2 by volume to form a synthetic solution, heated in a water bath to 50-80 ℃, reacted for 8-10 hours, the solid phase product was filtered, and dried in an incubator at 40-50 ℃ for 5-7 hours to obtain 4-acetamidobenzotriazole;

[0035] a2. 4-acetamidobenzotriazole and manganese nitrate are added to deionized water and mixed to form an impregnation solution, wherein the amount of 4-acetamidobenzotriazole added per liter of the impregnation solution is 50-80g and the amount of manganese nitrate added is 30-50g; the ferric chloride sample is added to deionized water and mixed to form a ferric chloride solution with a concentration of 20-40g / L; the foamed iron is immersed in the impregnation solution (the weight of the foamed iron immersed in the impregnation solution per liter is 70-110g), and after dipping for 15-30 minutes, a certain amount of ferric chloride solution is added (the volume ratio between the ferric chloride solution and the impregnation solution is 1-3:5-7), and the impregnation is continued for 2-4 hours. The foamed iron sample is taken out and dried at room temperature for 48-72 hours to obtain a surface loaded with five 4-acetamidobenzotriazole manganese [Mn(4-CH3CONH-BTA)5] foamed iron, which is recorded as intermediate A.

[0036] Step [2] converts the manganese pentadienyl 4-acetamidobenzotriazole [Mn(4-CH3CONH-BTA)5] on the surface of the foamed iron substrate into manganese pentadienyl 5-nitro-4-acetamidobenzotriazole [Mn(5-NO2-4-CH3CONH-BTA)5] through a substitution reaction, specifically comprising the following operations:

[0037] b1. A nitric acid solution having a concentration of 68% was added to deionized water to form a nitric acid solution having a mass concentration of 7 to 12%; ethyl nitrate was added to ethanol and mixed to form a concentration of 15 to 40 mL / L of ethyl nitrate solution; a nitric acid solution was added to the ethyl nitrate solution in a volume ratio of 3 to 5: 1 to 2, and the mixture was mixed to form a nitro-substituted solution;

[0038] b2. The intermediate A is immersed in the nitro substitution solution (the weight of the intermediate A immersed in each liter of the nitro substitution solution is 160-180 g), and the reaction is carried out at a water bath temperature of 20-30°C for 0.5-1.5 hours to convert the penta-4-acetamidobenzotriazole manganese [Mn(4-CH3CONH-BTA)5] into penta-5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5] through the substitution reaction. The foamed iron sample is taken out and dried at room temperature for 6-10 hours to obtain foamed iron with penta-5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5] loaded on the surface, which is recorded as intermediate B.

[0039] Step [3] Ba2Cu2Gd3Mn2O is loaded on the surface of penta-5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5] 12 Crystal, specifically including the following operations:

[0040] c1. Add barium chloride, copper chloride, gadolinium nitrate, potassium permanganate and ammonium bisulfate to deionized water and mix to form a crystallization solution having a barium chloride concentration of 30 to 50 g / L, a copper chloride concentration of 40 to 90 g / L, a gadolinium nitrate concentration of 100 to 140 g / L, a potassium permanganate concentration of 40 to 70 g / L, and an ammonium bisulfate concentration of 20 to 30 g / L;

[0041] c2. Immerse the intermediate B in the crystallization solution (the weight of the intermediate B immersed in each liter of the crystallization solution is 120-140 g), heat to 60-90 ° C, react for 6-8 hours, rinse with deionized water several times, and dry at room temperature for 12-16 hours to complete Ba2Cu2Gd3Mn2O 12The crystal was loaded on the surface of five 5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5], and finally the composite material (foamed iron-based five 5-nitro-4-acetamidobenzotriazole manganese loaded Ba2Cu2Gd3Mn2O 12 ), and its microstructure diagram is shown as Figure 2 shown.

[0042] The preferred embodiments of the present invention are described below with examples.

[0043] Example 1

[0044] Preferred embodiment 1 of the present invention provides a method for preparing a composite material for ozone photocatalytic synergistic treatment of unsymmetrical dimethylhydrazine wastewater, comprising the following steps:

[0045] Step [1] loading penta-4-acetamidobenzotriazole manganese [Mn(4-CH3CONH-BTA)5] organic matter on the surface of the foamed iron matrix specifically includes the following operations:

[0046] a1. Benzotriazole, acetic acid and n-propylamine were added to deionized water and mixed to form a base solution, wherein the amount of benzotriazole added per liter of the base solution was 25 g, acetic acid was added in an amount of 70 mL, and n-propylamine was added in an amount of 80 mL; tert-butyl perbenzoate was added to ethanol and mixed to form an additive solution, wherein the amount of tert-butyl perbenzoate added per liter of the additive solution was 80 mL; the base solution and the additive solution were mixed in a volume ratio of 7:2 to form a synthetic solution, heated in a water bath to 80 ° C, reacted for 9 hours, the solid phase product was filtered and dried in an incubator at 50 ° C for 7 hours to obtain 4-acetamidobenzotriazole;

[0047] a2. 4-acetamidobenzotriazole and manganese nitrate are added to deionized water and mixed to form an impregnation solution, wherein the 4-acetamidobenzotriazole addition amount is 70g and the manganese nitrate addition amount is 50g per liter of the impregnation solution; the ferric chloride sample is added to deionized water and mixed to form a ferric chloride solution with a concentration of 40g / L; the foamed iron is immersed in the impregnation solution (the weight of the foamed iron immersed in the impregnation solution per liter is 100g), and after dipping for 25 minutes, a certain amount of ferric chloride solution (the volume ratio between the ferric chloride solution and the impregnation solution is 3:5) is added, and the impregnation is continued for 3 hours. The foamed iron sample is taken out and dried at room temperature for 65 hours to obtain a surface-loaded iron foam with five 4-acetamidobenzotriazole manganese compounds [Mn(4-CH3CONH-BTA)5], which is designated as intermediate A.

[0048] Step [2] converts the manganese pentadienyl 4-acetamidobenzotriazole [Mn(4-CH3CONH-BTA)5] on the surface of the foamed iron substrate into manganese pentadienyl 5-nitro-4-acetamidobenzotriazole [Mn(5-NO2-4-CH3CONH-BTA)5] through a substitution reaction, specifically comprising the following operations:

[0049] b1. A nitric acid solution having a concentration of 68% was added to deionized water to form a nitric acid solution having a mass concentration of 10%; ethyl nitrate was added to ethanol and mixed to form a concentration of 30mL / L ethyl nitrate solution; a nitric acid solution was added to the ethyl nitrate solution in a ratio of 4:1 by volume, and the mixture was mixed to form a nitro-substituted solution;

[0050] b2. The intermediate A is immersed in the nitro substitution solution (the weight of the intermediate A immersed in each liter of the nitro substitution solution is 170 g), and the reaction is carried out in a water bath temperature of 25°C for 1 hour to convert the penta-4-acetamidobenzotriazole manganese [Mn(4-CH3CONH-BTA)5] into penta-5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5] through the substitution reaction. The foamed iron sample is taken out and dried at room temperature for 9 hours to obtain foamed iron with penta-5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5] loaded on the surface, which is recorded as intermediate B.

[0051] Step [3] Ba2Cu2Gd3Mn2O is loaded on the surface of penta-5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5] 12 Crystal, specifically including the following operations:

[0052] c1. Barium chloride, copper chloride, gadolinium nitrate, potassium permanganate and ammonium bisulfate were added to deionized water and mixed to form a barium chloride concentration of 45g / L, a copper chloride concentration of 80g / L, a gadolinium nitrate concentration of 130g / L, a potassium permanganate concentration of 60g / L, and an ammonium bisulfate concentration of 25g / L of crystallization liquid;

[0053] 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 130 g), heated to 80 ° C, reacted for 8 hours, washed three times with deionized water, and dried at room temperature for 14 hours to complete Ba2Cu2Gd3Mn2O 12 The crystal was loaded on the surface of five 5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5], and finally the composite material (foamed iron-based five 5-nitro-4-acetamidobenzotriazole manganese loaded Ba2Cu2Gd3Mn2O 12), recorded as Example 1.

[0054] Comparative Example 1

[0055] This comparative example 1 provides a method for preparing a composite material for ozone photocatalytic synergistic treatment of unsymmetrical dimethylhydrazine wastewater, comprising the following steps:

[0056] Step [1] loading penta-4-acetamidobenzotriazole manganese [Mn(4-CH3CONH-BTA)5] organic matter on the surface of the foamed iron matrix specifically includes the following operations:

[0057] a1. Benzotriazole, acetic acid and n-propylamine were added to deionized water and mixed to form a base solution, wherein the amount of benzotriazole added per liter of the base solution was 12 g, acetic acid was added in an amount of 55 mL, and n-propylamine was added in an amount of 70 mL; tert-butyl perbenzoate was added to ethanol and mixed to form an additive solution, wherein the amount of tert-butyl perbenzoate added per liter of the additive solution was 40 mL; the base solution and the additive solution were mixed in a ratio of 5:1 by volume to form a synthetic solution, heated in a water bath to 60 ° C, reacted for 9 hours, the solid phase product was filtered, and dried in an incubator at 45 ° C for 5 hours to obtain 4-acetamidobenzotriazole;

[0058] a2. 4-acetamidobenzotriazole and manganese nitrate are added to deionized water and mixed to form an impregnation solution, wherein the 4-acetamidobenzotriazole addition amount is 60g and the manganese nitrate addition amount is 40g per liter of the impregnation solution; the ferric chloride sample is added to deionized water and mixed to form a ferric chloride solution with a concentration of 30g / L; the foamed iron is immersed in the impregnation solution (the weight of the foamed iron immersed in the impregnation solution per liter is 80g), and after dipping for 20 minutes, a certain amount of ferric chloride solution (the volume ratio between the ferric chloride solution and the impregnation solution is 2:5) is added, and the impregnation is continued for 2 hours. The foamed iron sample is taken out and dried at room temperature for 48 hours to obtain a surface-loaded iron foam with five 4-acetamidobenzotriazole manganese compounds [Mn(4-CH3CONH-BTA)5], which is designated as intermediate A.

[0059] Step [2] Ba2Cu2Gd3Mn2O is loaded on the surface of penta-4-acetamidobenzotriazole manganese [Mn(4-CH3CONH-BTA)5] 12 Crystal, specifically including the following operations:

[0060] c1. Barium chloride, copper chloride, gadolinium nitrate, potassium permanganate and ammonium bisulfate were added to deionized water and mixed to form a barium chloride concentration of 35g / L, a copper chloride concentration of 50g / L, a gadolinium nitrate concentration of 110g / L, a potassium permanganate concentration of 50g / L, and an ammonium bisulfate concentration of 22g / L of a crystallization solution;

[0061] 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 130 g), heated to 70°C, reacted for 7 hours, washed twice with deionized water, and dried at room temperature for 13 hours to complete Ba2Cu2Gd3Mn2O 12 The crystals were loaded on the surface of five 4-acetamidobenzotriazole manganese [Mn (4-CH3CONH-BTA) 5] to finally obtain the composite material (foamed iron-based five 4-acetamidobenzotriazole manganese [Mn (4-CH3CONH-BTA) 5] loaded with Ba2Cu2Gd3Mn2O 12 ), recorded as comparative example 1.

[0062] Comparative Example 2

[0063] This comparative example 2 provides a method for preparing a composite material for ozone photocatalytic synergistic treatment of unsymmetrical dimethylhydrazine wastewater, comprising the following steps:

[0064] Step [1] loading penta-4-acetamidobenzotriazole manganese [Mn(4-CH3CONH-BTA)5] organic matter on the surface of the foamed iron matrix specifically includes the following operations:

[0065] a1. Benzotriazole, acetic acid and n-propylamine were added to deionized water and mixed to form a base solution, wherein the amount of benzotriazole added per liter of the base solution was 14 g, acetic acid was added in an amount of 60 mL, and n-propylamine was added in an amount of 70 mL; tert-butyl perbenzoate was added to ethanol and mixed to form an additive solution, wherein the amount of tert-butyl perbenzoate added per liter of the additive solution was 60 mL; the base solution and the additive solution were mixed in a ratio of 7:2 by volume to form a synthetic solution, heated in a water bath to 70 ° C, reacted for 10 hours, the solid phase product was filtered, and dried in an incubator at 46 ° C for 6 hours to obtain 4-acetamidobenzotriazole;

[0066] a2. 4-acetamidobenzotriazole and manganese nitrate are added to deionized water and mixed to form an impregnation solution, wherein the addition amount of 4-acetamidobenzotriazole and manganese nitrate per liter of the impregnation solution is 70g and the addition amount of manganese nitrate is 40g; the ferric chloride sample is added to deionized water and mixed to form a ferric chloride solution with a concentration of 30g / L; the foamed iron is immersed in the impregnation solution (the weight of the foamed iron immersed in the impregnation solution per liter is 90g), and after dipping for 20 minutes, a certain amount of ferric chloride solution is added (the volume ratio between the ferric chloride solution and the impregnation solution is 3:5), and the impregnation is continued for 3 hours. The foamed iron sample is taken out and dried at room temperature for 60 hours to obtain a surface-loaded iron foam with five 4-acetamidobenzotriazole manganese compounds [Mn(4-CH3CONH-BTA)5], which is designated as intermediate A.

[0067] Step [2] converts the manganese pentadienyl 4-acetamidobenzotriazole [Mn(4-CH3CONH-BTA)5] on the surface of the foamed iron substrate into manganese pentadienyl 5-nitro-4-acetamidobenzotriazole [Mn(5-NO2-4-CH3CONH-BTA)5] through a substitution reaction, specifically comprising the following operations:

[0068] b1. A nitric acid solution having a concentration of 68% was added to deionized water to form a nitric acid solution having a mass concentration of 8%; ethyl nitrate was added to ethanol and mixed to form a concentration of 20 mL / L of ethyl nitrate solution; the nitric acid solution was added to the ethyl nitrate solution in a volume ratio of 5:2, and the mixture was mixed to form a nitro-substituted solution;

[0069] b2. The intermediate A was immersed in the nitro substitution solution (the weight of the intermediate A immersed in each liter of the nitro substitution solution was 170 g), and the reaction was carried out at a water bath temperature of 22°C for 1 hour to convert penta-4-acetamidobenzotriazole manganese [Mn(4-CH3CONH-BTA)5] into penta-5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5] through the substitution reaction. The foamed iron sample was taken out and dried at room temperature for 8 hours to obtain foamed iron with penta-5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5] loaded on the surface, which was recorded as Comparative Example 2.

[0070] In order to analyze the performance of ozone / photocatalytic synergistic oxidation degradation of UDMH-containing wastewater in Example 1, Comparative Example 1 and Comparative Example 2, UDMH was added to deionized water to form simulated UDMH-containing wastewater with UDMH concentrations of 5 mg / L and 10 mg / L, respectively. 100 ml of simulated UDMH-containing wastewater was poured into a beaker, and 10 g of Example 1, Comparative Example 1 and Comparative Example 2 were respectively placed in the beaker. Ozone with a concentration of 10 mg / L generated by an ozone generator was input into each simulated UDMH-containing wastewater at a flow rate of 50 ml / min. At the same time, a xenon lamp light source was used to irradiate Comparative Example 1, Comparative Example 2 and Example 1 for thirty minutes under the conditions of an operating current of 22 A and an operating voltage of 14 V. The results were compared with those of the simulated UDMH-containing wastewater by ozone degradation alone, visible light degradation alone and ultraviolet photocatalytic degradation alone. The UDMH concentration of the simulated UDMH-containing wastewater was measured by sodium aminoferrocyanide spectrophotometry (national standard GB / T14376-1993). The relative concentrations of residual UDMH in Example 1, Comparative Example 1 and Comparative Example 2 were 10 mg / L and 5 mg / L respectively, and the degradation concentrations were as follows: Figure 3 and Figure 4As shown in the figure, it can be seen that the relative concentrations of residual UDMH in Example 1 of the simulated UDMH-containing wastewater with ultraviolet and visible light photocatalytic synergistic ozone oxidation degradation concentrations of 10 mg / L and 5 mg / L are only 0.08, 0.04 and 0.1, 0.07, respectively, which are not only much lower than 0.39, 0.34 and 0.43, 0.4 of Comparative Example 2, but also lower than 0.21, 0.17 and 0.27, 0.24 of Comparative Example 1, and also significantly lower than 0.39, 0.32 of ozone degradation alone, lower than 0.34, 0.32 of visible light catalytic degradation only, and lower than 0.29, 0.27 of ultraviolet light catalytic degradation only.

[0071] In summary, the composite material prepared according to the present invention has the performance of wide spectral response and high efficiency in photocatalytic synergistic ozone oxidation degradation of unsymmetrical dimethylhydrazine wastewater.

[0072] To illustrate in further detail, three additional examples are provided below.

[0073] Example 2

[0074] Preferred embodiment 2 of the present invention provides a method for preparing a composite material for ozone photocatalytic synergistic treatment of unsymmetrical dimethylhydrazine wastewater, comprising the following steps:

[0075] Step [1] loading penta-4-acetamidobenzotriazole manganese [Mn(4-CH3CONH-BTA)5] organic matter on the surface of the foamed iron matrix specifically includes the following operations:

[0076] a1. Benzotriazole, acetic acid and n-propylamine were added to deionized water and mixed to form a base solution, wherein the amount of benzotriazole added per liter of the base solution was 10 g, acetic acid was added in an amount of 50 mL, and n-propylamine was added in an amount of 90 mL; tert-butyl perbenzoate was added to ethanol and mixed to form an additive solution, wherein the amount of tert-butyl perbenzoate added per liter of the additive solution was 30 mL; the base solution and the additive solution were mixed in a ratio of 5:2 by volume to form a synthetic solution, heated in a water bath to 50 ° C, reacted for 10 hours, the solid phase product was filtered, and dried in an incubator at 50 ° C for 5 hours to obtain 4-acetamidobenzotriazole;

[0077] a2. 4-acetamidobenzotriazole and manganese nitrate are added to deionized water and mixed to form an impregnation solution, wherein the addition amount of 4-acetamidobenzotriazole is 50g and the addition amount of manganese nitrate is 30g per liter of the impregnation solution; a ferric chloride sample is added to deionized water and mixed to form a ferric chloride solution with a concentration of 40g / L; foamed iron is immersed in the impregnation solution (the weight of the foamed iron immersed in the impregnation solution per liter is 70g), and after dipping for 15 minutes, a certain amount of ferric chloride solution (the volume ratio between the ferric chloride solution and the impregnation solution is 3:7) is added, and the impregnation is continued for 2 hours. The foamed iron sample is taken out and dried at room temperature for 48 hours to obtain a surface-loaded iron foam with five 4-acetamidobenzotriazole manganese compounds [Mn(4-CH3CONH-BTA)5], which is designated as intermediate A.

[0078] Step [2] converts the manganese pentadienyl 4-acetamidobenzotriazole [Mn(4-CH3CONH-BTA)5] on the surface of the foamed iron substrate into manganese pentadienyl 5-nitro-4-acetamidobenzotriazole [Mn(5-NO2-4-CH3CONH-BTA)5] through a substitution reaction, specifically comprising the following operations:

[0079] b1. A 68% concentrated nitric acid solution was added to deionized water to form a 7% nitric acid solution; ethyl nitrate was added to ethanol and mixed to form a concentration of 15mL / L ethyl nitrate solution; the nitric acid solution was added to the ethyl nitrate solution in a volume ratio of 3:2, and the mixture was mixed to form a nitro-substituted solution;

[0080] b2. The intermediate A is immersed in the nitro substitution solution (the weight of the intermediate A immersed in each liter of the nitro substitution solution is 160 g), and the reaction is carried out at a water bath temperature of 20°C for 1.5 hours to convert penta-4-acetamidobenzotriazole manganese [Mn(4-CH3CONH-BTA)5] into penta-5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5] through the substitution reaction. The foamed iron sample is taken out and dried at room temperature for 6 hours to obtain foamed iron with penta-5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5] loaded on the surface, which is recorded as intermediate B.

[0081] Step [3] Ba2Cu2Gd3Mn2O is loaded on the surface of penta-5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5] 12 Crystal, specifically including the following operations:

[0082] c1. Barium chloride, copper chloride, gadolinium nitrate, potassium permanganate and ammonium bisulfate were added to deionized water and mixed to form a barium chloride concentration of 50 g / L, a copper chloride concentration of 40 g / L, a gadolinium nitrate concentration of 140 g / L, a potassium permanganate concentration of 40 g / L, and an ammonium bisulfate concentration of 20 g / L of crystallization liquid;

[0083] 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 120 g), heated to 60°C, reacted for 8 hours, washed twice with deionized water, and dried at room temperature for 16 hours to complete Ba2Cu2Gd3Mn2O 12 The crystal was loaded on the surface of five 5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5], and finally the composite material (foamed iron-based five 5-nitro-4-acetamidobenzotriazole manganese loaded Ba2Cu2Gd3Mn2O 12 ).

[0084] Example 3

[0085] Preferred embodiment 3 of the present invention provides a method for preparing a composite material for ozone photocatalytic synergistic treatment of unsymmetrical dimethylhydrazine wastewater, comprising the following steps:

[0086] Step [1] loading penta-4-acetamidobenzotriazole manganese [Mn(4-CH3CONH-BTA)5] organic matter on the surface of the foamed iron matrix specifically includes the following operations:

[0087] a1. Benzotriazole, acetic acid and n-propylamine were added to deionized water and mixed to form a base solution, wherein the amount of benzotriazole added per liter of the base solution was 30 g, the amount of acetic acid added was 80 mL, and the amount of n-propylamine added was 60 mL; tert-butyl perbenzoate was added to ethanol and mixed to form an additive solution, wherein the amount of tert-butyl perbenzoate added per liter of the additive solution was 90 mL; the base solution and the additive solution were mixed in a ratio of 9:1 by volume to form a synthetic solution, heated in a water bath to 80 ° C, reacted for 8 hours, the solid phase product was filtered, and dried in an incubator at 40 ° C for 7 hours to obtain 4-acetamidobenzotriazole;

[0088] a2. 4-acetamidobenzotriazole and manganese nitrate are added to deionized water and mixed to form an impregnation solution, wherein the addition amount of 4-acetamidobenzotriazole and manganese nitrate per liter of the impregnation solution is 80g and the addition amount of manganese nitrate is 50g; a ferric chloride sample is added to deionized water and mixed to form a ferric chloride solution with a concentration of 20g / L; foamed iron is immersed in the impregnation solution (the weight of the foamed iron immersed in the impregnation solution per liter is 110g), and after dipping for 30 minutes, a certain amount of ferric chloride solution is added (the volume ratio between the ferric chloride solution and the impregnation solution is 1:5), and the impregnation is continued for 4 hours. The foamed iron sample is taken out and dried at room temperature for 72 hours to obtain a surface-loaded iron foam with five 4-acetamidobenzotriazole manganese [Mn(4-CH3CONH-BTA)5], which is recorded as intermediate A.

[0089] Step [2] converts the manganese pentadienyl 4-acetamidobenzotriazole [Mn(4-CH3CONH-BTA)5] on the surface of the foamed iron substrate into manganese pentadienyl 5-nitro-4-acetamidobenzotriazole [Mn(5-NO2-4-CH3CONH-BTA)5] through a substitution reaction, specifically comprising the following operations:

[0090] b1. A nitric acid solution having a concentration of 68% was added to deionized water to form a nitric acid solution having a mass concentration of 12%; ethyl nitrate was added to ethanol and mixed to form a concentration of 40mL / L of ethyl nitrate solution; the nitric acid solution was added to the ethyl nitrate solution in a volume ratio of 5:1, and the mixture was mixed to form a nitro-substituted solution;

[0091] b2. The intermediate A is immersed in the nitro substitution solution (the weight of the intermediate A immersed in each liter of the nitro substitution solution is 180 g), and the reaction is carried out at a water bath temperature of 30°C for 0.5 hour to convert the penta-4-acetamidobenzotriazole manganese [Mn(4-CH3CONH-BTA)5] into penta-5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5] through the substitution reaction. The foamed iron sample is taken out and dried at room temperature for 10 hours to obtain foamed iron with penta-5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5] loaded on the surface, which is recorded as intermediate B.

[0092] Step [3] Ba2Cu2Gd3Mn2O is loaded on the surface of penta-5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5] 12 Crystal, specifically including the following operations:

[0093] c1. Barium chloride, copper chloride, gadolinium nitrate, potassium permanganate and ammonium bisulfate were added to deionized water and mixed to form a barium chloride concentration of 30 g / L, a copper chloride concentration of 90 g / L, a gadolinium nitrate concentration of 100 g / L, a potassium permanganate concentration of 70 g / L, and an ammonium bisulfate concentration of 30 g / L of a crystallization solution;

[0094] 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 140 g), heated to 90 ° C, reacted for 6 hours, washed three times with deionized water, and dried at room temperature for 12 hours to complete Ba2Cu2Gd3Mn2O 12 The crystal was loaded on the surface of five 5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5], and finally the composite material (foamed iron-based five 5-nitro-4-acetamidobenzotriazole manganese loaded Ba2Cu2Gd3Mn2O 12 ).

[0095] Example 4

[0096] Preferred embodiment 4 of the present invention provides a method for preparing a composite material for ozone photocatalytic synergistic treatment of unsymmetrical dimethylhydrazine wastewater, comprising the following steps:

[0097] Step [1] loading penta-4-acetamidobenzotriazole manganese [Mn(4-CH3CONH-BTA)5] organic matter on the surface of the foamed iron matrix specifically includes the following operations:

[0098] a1. Benzotriazole, acetic acid and n-propylamine were added to deionized water and mixed to form a base solution, wherein the amount of benzotriazole added per liter of the base solution was 20 g, acetic acid was added in an amount of 65 mL, and n-propylamine was added in an amount of 75 mL; tert-butyl perbenzoate was added to ethanol and mixed to form an additive solution, wherein the amount of tert-butyl perbenzoate added per liter of the additive solution was 60 mL; the base solution and the additive solution were mixed in a ratio of 7:2 by volume to form a synthetic solution, heated in a water bath to 65 ° C, reacted for 9 hours, the solid phase product was filtered, and dried in an incubator at 45 ° C for 6 hours to obtain 4-acetamidobenzotriazole;

[0099] a2. 4-acetamidobenzotriazole and manganese nitrate are added to deionized water and mixed to form an impregnation solution, wherein the addition amount of 4-acetamidobenzotriazole is 65g and the addition amount of manganese nitrate is 40g per liter of the impregnation solution; a ferric chloride sample is added to deionized water and mixed to form a ferric chloride solution with a concentration of 30g / L; foamed iron is immersed in the impregnation solution (the weight of the foamed iron immersed in the impregnation solution per liter is 90g), and after dipping for 23 minutes, a certain amount of ferric chloride solution is added (the volume ratio between the ferric chloride solution and the impregnation solution is 3:5), and the impregnation is continued for 3 hours. The foamed iron sample is taken out and dried at room temperature for 60 hours to obtain a surface-loaded iron foam with five 4-acetamidobenzotriazole manganese compounds [Mn(4-CH3CONH-BTA)5], which is designated as intermediate A.

[0100] Step [2] converts the manganese pentadienyl 4-acetamidobenzotriazole [Mn(4-CH3CONH-BTA)5] on the surface of the foamed iron substrate into manganese pentadienyl 5-nitro-4-acetamidobenzotriazole [Mn(5-NO2-4-CH3CONH-BTA)5] through a substitution reaction, specifically comprising the following operations:

[0101] b1. A nitric acid solution having a concentration of 68% was added to deionized water to form a nitric acid solution having a mass concentration of 10%; ethyl nitrate was added to ethanol and mixed to form a concentration of 26mL / L of ethyl nitrate solution; a nitric acid solution was added to the ethyl nitrate solution in a volume ratio of 4:1, and the mixture was mixed to form a nitro-substituted solution;

[0102] b2. The intermediate A is immersed in the nitro substitution solution (the weight of the intermediate A immersed in each liter of the nitro substitution solution is 170 g), and the reaction is carried out in a water bath temperature of 25°C for 1 hour to convert the penta-4-acetamidobenzotriazole manganese [Mn(4-CH3CONH-BTA)5] into penta-5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5] through the substitution reaction. The foamed iron sample is taken out and dried at room temperature for 9 hours to obtain foamed iron with penta-5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5] loaded on the surface, which is recorded as intermediate B.

[0103] Step [3] Ba2Cu2Gd3Mn2O is loaded on the surface of penta-5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5] 12 Crystal, specifically including the following operations:

[0104] c1. Barium chloride, copper chloride, gadolinium nitrate, potassium permanganate and ammonium bisulfate were added to deionized water and mixed to form a barium chloride concentration of 40g / L, a copper chloride concentration of 65g / L, a gadolinium nitrate concentration of 120g / L, a potassium permanganate concentration of 55g / L, and an ammonium bisulfate concentration of 25g / L of crystallization liquid;

[0105] 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 130 g), heated to 75 ° C, reacted for 7 hours, washed three times with deionized water, and dried at room temperature for 14 hours to complete Ba2Cu2Gd3Mn2O 12 The crystal was loaded on the surface of five 5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5], and finally the composite material (foamed iron-based five 5-nitro-4-acetamidobenzotriazole manganese loaded Ba2Cu2Gd3Mn2O 12 ).

[0106] The above are only 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 core ideas of the present invention, and is not used to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, etc. made within the ideas and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing a composite material for ozone photocatalytic synergistic treatment of unsymmetrical dimethylhydrazine wastewater, characterized in that: The following steps are included: Step [1] Loading penta-4-acetamidobenzotriazole manganese [Mn(4-CH3CONH-BTA)5] organic matter on the surface of the foamed iron matrix; Step [2] converting the manganese pentadienyl 4-acetamidobenzotriazole [Mn(4-CH3CONH-BTA)5] on the surface of the foamed iron substrate into manganese pentadienyl 5-nitro-4-acetamidobenzotriazole [Mn(5-NO2-4-CH3CONH-BTA)5] through a substitution reaction; Step [3] Ba2Cu2Gd3Mn2O is loaded on the surface of penta-5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5] 12 crystal.

2. The method for preparing a composite material for ozone photocatalytic synergistic treatment of unsymmetrical dimethylhydrazine wastewater according to claim 1, characterized in that: The step [1] specifically includes the following operations: a1. Benzotriazole, acetic acid, and n-propylamine were added to deionized water and mixed to form a base solution; tert-butyl peroxybenzoate was added to ethanol and mixed to form an additive solution; the base solution and the additive solution were mixed in a certain proportion to form a synthetic solution, heated in a water bath to 50-80°C, reacted for 8-10 hours, the solid phase product was filtered, and dried in an incubator at 40-50°C for 5-7 hours to obtain 4-acetamidobenzotriazole; a2. 4-acetamidobenzotriazole and manganese nitrate were added to deionized water and mixed to form an impregnation solution; a ferric chloride sample was added to deionized water and mixed to form a ferric chloride solution; an iron foam was immersed in the impregnation solution for 15-30 minutes, after which a certain amount of ferric chloride solution was added and the immersion was continued for 2-4 hours. The iron foam sample was removed and dried at room temperature for 48-72 hours to obtain an iron foam with penta-4-acetamidobenzotriazole manganese complex [Mn(4-CH3CONH-BTA)5] loaded on its surface, which was recorded as intermediate A.

3. The method for preparing a composite material for ozone-photocatalytic synergistic treatment of unsymmetrical dimethylhydrazine wastewater according to claim 2, characterized in that: In step a1, the amount of benzotriazole added to each liter of the base liquid is 10-30 g, the amount of acetic acid added is 50-80 mL, and the amount of n-propylamine added is 60-90 mL; the amount of tert-butyl perbenzoate added to each liter of the additive liquid is 30-90 mL; and the volume ratio between the base liquid and the additive liquid in the synthetic liquid is 5-9:1-2.

4. The method for preparing a composite material for ozone-photocatalytic synergistic treatment of unsymmetrical dimethylhydrazine wastewater according to claim 2, characterized in that: In step a2, the amount of 4-acetamidobenzotriazole added to each liter of the impregnation solution is 50-80 g, and the amount of manganese nitrate added is 30-50 g; the concentration of the ferric chloride solution is 20-40 g / L; the weight of the foamed iron immersed in each liter of the impregnation solution is 70-110 g; and the volume ratio of the ferric chloride solution to the impregnation solution is 1-3:5-7.

5. The method for preparing a composite material for ozone photocatalytic synergistic treatment of unsymmetrical dimethylhydrazine wastewater according to claim 2, characterized in that: The step [2] specifically includes the following operations: b1. A 68% concentrated nitric acid concentration was added to deionized water to form a nitric acid solution; ethyl nitrate was added to ethanol and mixed to form an ethyl nitrate solution; a nitric acid solution was added to the ethyl nitrate solution in a certain proportion, and the mixture was mixed to form a nitro-substituted solution; b2. The intermediate A is immersed in the nitro substitution solution and reacted at a water bath temperature of 20-30°C for 0.5-1.5 hours to convert penta-4-acetamidobenzotriazole manganese [Mn(4-CH3CONH-BTA)5] into penta-5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5] through the substitution reaction. The foamed iron sample is taken out and dried at room temperature for 6-10 hours to obtain foamed iron with penta-5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5] loaded on the surface, which is recorded as intermediate B.

6. The method for preparing a composite material for ozone-photocatalytic synergistic treatment of unsymmetrical dimethylhydrazine wastewater according to claim 5, characterized in that: In step b1, the mass concentration of the nitric acid solution is 7-12%; the concentration of the ethyl nitrate solution is 15-40 mL / L; and the volume ratio between the nitric acid solution and the ethyl nitrate solution in the nitro-substituted solution is 3-5:1-2.

7. The method for preparing a composite material for ozone-photocatalytic synergistic treatment of unsymmetrical dimethylhydrazine wastewater according to claim 5, characterized in that: In step b2, the weight of the intermediate A immersed in each liter of the nitro substitution solution is 160-180 g.

8. The method for preparing a composite material for ozone-photocatalytic synergistic treatment of unsymmetrical dimethylhydrazine wastewater according to claim 5, characterized in that: The step [3] specifically includes the following operations: c1. Barium chloride, copper chloride, gadolinium nitrate, potassium permanganate and ammonium bisulfate were added to deionized water and mixed to form a crystallization solution; c2. The intermediate B was immersed in the crystallization solution, heated to 60~90 ° C, reacted for 6~8 hours, washed with deionized water several times, and dried at room temperature for 12~16 hours to complete Ba2Cu2Gd3Mn2O 12 The crystals are loaded on the surface of penta-5-nitro-4-acetamidobenzotriazole manganese [Mn(5-NO2-4-CH3CONH-BTA)5] to finally obtain the composite material.

9. The method for preparing a composite material for ozone-photocatalytic synergistic treatment of unsymmetrical dimethylhydrazine wastewater according to claim 8, characterized in that: In step c1, the concentration of barium chloride in the crystallization solution is 30-50 g / L, the concentration of copper chloride is 40-90 g / L, the concentration of gadolinium nitrate is 100-140 g / L, the concentration of potassium permanganate is 40-70 g / L, and the concentration of ammonium bisulfate is 20-30 g / L.

10. The method for preparing a composite material for ozone-photocatalytic synergistic treatment of unsymmetrical dimethylhydrazine wastewater according to claim 8, characterized in that: In step c2, the weight of the intermediate B immersed in each liter of the crystallization solution is 120-140 g.

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