A method for preparing a foam copper-based composite material with photothermal effect

Abstract

The application provides a preparation method of a foamed copper-based composite material with a photothermal effect, and comprises the following steps: step [1], loading nickel atom modified polydopamine / aniline composite organic matter on the surface of a foamed copper matrix; step [2], converting the nickel atom modified polydopamine / aniline composite organic matter on the surface of the foamed copper matrix into a Ni(PDA)2(PANI)2 coordination polymer; and step [3], loading CeCo2Fe 16 O 27 crystals on the surface of the Ni(PDA)2(PANI)2 coordination polymer. The foamed copper-based composite material prepared by the method has excellent photothermal effect and can efficiently activate peroxyacetic acid to degrade metronidazole wastewater.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of metronidazole wastewater treatment, and particularly relates to a preparation method of a foamed copper-based composite material with photothermal effect for treating metronidazole wastewater. BACKGROUND

[0002] Metronidazole is a drug with a nitro-imidazole ring structure, which is widely used in the field of antiprotozoal drugs to treat balantidiasis, cutaneous leishmaniasis, and guinea worm disease, etc.; and is also widely used in the field of antibiotic drugs to treat infections caused by anaerobic bacteria, including digestive system infections, respiratory system infections, bone tissue infections, reproductive system infections, etc., and is also used to treat inflammation caused by anaerobic bacteria, such as appendicitis, osteomyelitis, cholecystitis, and various diseases such as liver abscess, brain abscess and empyema. With the development of economy and the pharmaceutical industry, the demand and production and use of metronidazole are increasing, and a large amount of metronidazole-containing wastewater is generated in the production process of metronidazole. Metronidazole is soluble in water and difficult to biodegrade, and is easy to migrate. Metronidazole can damage the function of human and animal nerve cells, interfere with the metabolic process of human and animal nerve cells, and has neurotoxicity; at the same time, metronidazole can stimulate the gastrointestinal mucosa and damage the function of the digestive system, and has digestive toxicity, and can affect the production and metabolism of red blood cells, and has hemotoxicity, and can also cause allergic reactions in individuals, and has carcinogenicity. In summary, metronidazole wastewater poses a great threat to the water environment and society.

[0003] The activated peroxoacetic acid O-O bond can be broken to generate peroxoacetyl radicals CH3C(O)OO·, acetoxy radicals CH3C(O)O· and ·OH radicals with strong oxidizing properties, and these active radicals can degrade and treat metronidazole-containing wastewater. In addition, the photothermal effect of the photothermal material can promote the breaking of the peroxoacetic acid O-O bond, reduce the activation energy of peroxoacetic acid, and further promote the generation of CH3C(O)OO·, CH3C(O)O· and ·OH radicals, thereby improving the degradation efficiency of metronidazole.

[0004] At present, in the field of metronidazole wastewater treatment, there is an urgent need to develop a treatment material for degrading metronidazole wastewater, which has excellent photothermal effect and can efficiently activate peroxoacetic acid. SUMMARY

[0005] In order to overcome the shortcomings of the prior art, the present application provides a preparation method of a foamed copper-based composite material with photothermal effect, and the foamed copper-based composite material prepared by the method has excellent photothermal effect and can efficiently activate peroxoacetic acid to degrade metronidazole wastewater.

[0006] The technical scheme adopted by the present application to solve its technical problems is:

[0007] The present application provides a preparation method of a foamed copper-based composite material with photothermal effect, which comprises the following steps:

[0008] Step [1] loading nickel atom modified polydopamine / aniline composite organic matter on the surface of foam copper matrix;

[0009] Step [2] converting the nickel atom modified polydopamine / aniline composite organic matter on the surface of foam copper matrix into Ni(PDA)2(PANI)2 coordination polymer;

[0010] Step [3] loading CeCo2Fe 16 O 27 crystal.

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

[0012] a1. adding p-aminobenzoic acid, m-phenylenediamine, dopamine hydrochloride, aminoacetic acid and sodium hydroxide into deionized water to form a base solution; adding azobis (isopropyl cyano) into ethanol to form an additive solution; mixing the base solution and the additive solution in a certain proportion to form a reaction solution; immersing a foam copper sample into the reaction solution; heating to 110-130℃; reacting for 3-5 hours; taking out the sample and washing with deionized water to obtain foam copper loaded with polydopamine / aniline composite organic matter, denoted as intermediate A;

[0013] a2. adding bis (1,5-cyclooctadiene) nickel into tetrahydrofuran to form a modification solution; immersing the intermediate A into the modification solution; immersing at room temperature for 4-6 hours; taking out the sample and washing with deionized water; drying at room temperature for 8-12 hours to obtain foam copper loaded with nickel atom modified polydopamine / aniline composite organic matter, denoted as intermediate B.

[0014] Preferably, in step a1, the amount of p-aminobenzoic acid added in the base solution is 20-50g per liter, the amount of m-phenylenediamine added is 70-110g per liter, the amount of dopamine hydrochloride added is 80-100g per liter, the amount of aminoacetic acid added is 10-25g per liter, and the amount of sodium hydroxide added is 15-30g per liter; the amount of azobis (isopropyl cyano) added in the additive solution is 30-60g per liter; the volume ratio of the base solution to the additive solution in the reaction solution is 9-11:2-3; and the weight of the foam copper immersed in the reaction solution is 170-220g per liter.

[0015] Preferably, in step a2, the amount of bis (1,5-cyclooctadiene) nickel added in the modification solution is 10-25g per liter; and the weight of the intermediate A immersed in the modification solution is 50-70g per liter.

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

[0017] b1. adding nickel sulfate, N-methylaniline, sodium pyrosulfite and dopamine hydrochloride into deionized water to form a coordination polymer building solution;

[0018] b2. immersing the intermediate B into the coordination polymer building solution, heating in a water bath to 50-90 DEG C for 10-14 hours, drying at room temperature for 6-8 hours to obtain a foam copper with a surface loaded with Ni(PDA)2(PANI)2 coordination polymer, denoted as intermediate C.

[0019] Preferably, in step b1, the concentration of nickel sulfate in the polymer building solution is 50-80 g / L, the concentration of sodium pyrosulfite is 20-30 g / L, and the concentration of dopamine hydrochloride is 40-70 g / L; the amount of N-methylaniline added per liter of the polymer building solution is 10-50 ml.

[0020] Preferably, in step b2, the weight of the intermediate B immersed per liter of the coordination polymer building solution is 140-170 g.

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

[0022] c1. adding ceric sulfate, hexamine cobalt chloride, ferric chloride and concentrated nitric acid with a mass fraction of 68% into deionized water, mixing to form a crystallization solution;

[0023] c2. immersing the intermediate C into the crystallization solution, heating in a water bath to 50-70 DEG C for 10-16 hours, washing with deionized water, and drying at room temperature for 6-9 hours to complete the loading of CeCo2Fe 16 O 27 crystals on the surface of the Ni(PDA)2(PANI)2 coordination polymer, and finally obtaining the foam copper-based composite material.

[0024] Preferably, in step c1, the concentration of ceric sulfate in the crystallization solution is 50-80 g / L, the concentration of ferric chloride is 130-150 g / L, the mass fraction of nitric acid is 3-6%, and the amount of hexamine cobalt chloride added per liter of the crystallization solution is 80-120 g.

[0025] Preferably, in step c2, the weight of the intermediate C immersed per liter of the crystallization solution is 220-240 g.

[0026] The positive effect of the present application: the foam copper-based composite material prepared according to the method of the present application, first, a polydopamine / aniline composite organic matter is formed on the surface of the foam copper matrix, then a nickel atom modified polydopamine / aniline composite organic matter is obtained, then the nitrogen atoms of the NH2 groups and NH groups of the nickel atom modified polydopamine / aniline composite organic matter on the surface of the foam copper matrix share the lone pair of electrons with nickel ions to form a [Ni(PDA)2(PANI)2] coordination polymer with a complex three-dimensional space structure, and finally, a CeCo2Fe 16 O 27 crystal is loaded on the surface of the [Ni(PDA)2(PANI)2] coordination polymer. Among them, when the [Ni(PDA)2(PANI)2] coordination polymer is irradiated with a certain energy light, the electrons of the bonding π orbital will jump to the antibonding π* orbital, and when these excited state electrons return to the ground state, heat will be released, which has excellent photothermal effect; at the same time, the photothermal effect of the [Ni(PDA)2(PANI)2] coordination polymer can promote the rupture of the peracetic acid O-O bond to generate CH3C(O)OO·, CH3C(O)O· and ·OH free radicals; in addition, the chelation of the amino group and the aromatic ring of the [Ni(PDA)2(PANI)2] coordination polymer can effectively increase the oxidation degradation reaction rate of metronidazole. The CeCo2Fe 16 O 27 crystal is a hexagonal crystal, which can significantly accelerate the electron transfer rate of the metronidazole degradation process, thereby reducing the activation energy of peracetic acid, further promoting the generation speed and quantity of CH3C(O)OO·, CH3C(O)O· and ·OH free radicals, and effectively improving the degradation effect of metronidazole wastewater.

[0027] In summary, the foam copper-based composite material prepared according to the present application has excellent photothermal effect and can efficiently activate peracetic acid to degrade metronidazole wastewater. BRIEF DESCRIPTION OF DRAWINGS

[0028] Figure 1 is a preparation flowchart of the foam copper-based composite material of the present application;

[0029] Figure 2 is a microstructure diagram of the foam copper-based composite material of the present application;

[0030] Figure 3 is the photothermal temperature of Example 1, Comparative Example 1 and Comparative Example 2 after irradiation for 30 minutes under simulated sunlight during the treatment of simulated metronidazole-containing wastewater;

[0031] Figure 4 The metronidazole degradation rate of Example 1, Comparative Example 1 and Comparative Example 2 in treating simulated metronidazole-containing wastewater. DETAILED DESCRIPTION

[0032] Referring Figure 1 The application provides a preparation method of a foam copper-based composite material with a photothermal effect, comprising the following steps:

[0033] Step [1] loading nickel atom modified polydopamine / aniline composite organic matter on the surface of a foam copper matrix, specifically comprising the following operations:

[0034] a1. adding p-aminobenzoic acid, m-phenylenediamine, dopamine hydrochloride, aminoacetic acid and sodium hydroxide into deionized water to form a base solution, wherein the amount of p-aminobenzoic acid added in the base solution is 20-50 g, the amount of m-phenylenediamine added is 70-110 g, the amount of dopamine hydrochloride added is 80-100 g, the amount of aminoacetic acid added is 10-25 g, and the amount of sodium hydroxide added is 15-30 g per liter of the base solution; adding azobis (isopropyl cyano) cyanide into ethanol to form an additive solution, wherein the amount of azobis (isopropyl cyano) cyanide added in the additive solution is 30-60 g per liter of the additive solution; mixing the base solution and the additive solution in a volume ratio of 9-11:2-3 to form a reaction solution, immersing a foam copper sample into the reaction solution (the weight of the foam copper immersed in the reaction solution is 170-220 g per liter of the reaction solution), heating to 110-130 DEG C, and reacting for 3-5 hours; after taking out the sample, washing with deionized water to obtain foam copper loaded with polydopamine / aniline (PDA / PANI) composite organic matter, denoted as intermediate A, wherein the structure of the polydopamine / aniline composite organic matter is as follows:

[0035]

[0036] a2. adding bis (1, 5-cyclooctadiene) nickel into tetrahydrofuran to form a modification solution, wherein the amount of bis (1, 5-cyclooctadiene) nickel added in the modification solution is 10-25 g per liter of the modification solution; immersing the intermediate A into the modification solution (the weight of the intermediate A immersed in the modification solution is 50-70 g per liter of the modification solution), and immersing at room temperature for 4-6 hours; after taking out the sample, washing with deionized water and drying at room temperature for 8-12 hours to obtain foam copper loaded with nickel atom modified polydopamine / aniline composite organic matter, denoted as intermediate B, wherein the structure of the nickel atom modified polydopamine / aniline composite organic matter is as follows:

[0037]

[0038] Step [2] converting the nickel atom modified polydopamine / aniline composite organic matter on the surface of the foam copper matrix into a Ni (PDA) 2 (PANI) 2 coordination polymer, specifically comprising the following operations:

[0039] b1. adding nickel sulfate, N-methylaniline, sodium pyrosulfite and dopamine hydrochloride into deionized water to form a coordination polymer building solution (the concentration of nickel sulfate in the polymer building solution is 50-80 g / L, the concentration of sodium pyrosulfite is 20-30 g / L, the concentration of dopamine hydrochloride is 40-70 g / L, and the amount of N-methylaniline added in each liter of the polymer building solution is 10-50 ml);

[0040] b2. immersing the intermediate B in the coordination polymer building solution (the weight of the intermediate B immersed in each liter of the coordination polymer building solution is 140-170 g), heating in a water bath to 50-90℃, reacting for 10-14 hours, and drying at room temperature for 6-8 hours to obtain a foam copper loaded with a Ni(PDA)2(PANI)2 coordination polymer, denoted as intermediate C.

[0041] Step [3] loading CeCo2Fe 16 O 27 crystals on the surface of the Ni(PDA)2(PANI)2 coordination polymer, specifically including the following operations:

[0042] c1. adding ceric sulfate, hexamine cobalt trichloride, ferric chloride and concentrated nitric acid with a mass fraction of 68% into deionized water and mixing to form a crystallization solution (the concentration of ceric sulfate in the crystallization solution is 50-80 g / L, the concentration of ferric chloride is 130-150 g / L, the mass fraction of nitric acid is 3-6%, and the amount of hexamine cobalt trichloride added in each liter of the crystallization solution is 80-120 g);

[0043] c2. immersing the intermediate C in the crystallization solution (the weight of the intermediate C immersed in each liter of the crystallization solution is 220-240 g), heating in a water bath to 50-70℃, reacting for 10-16 hours, washing with deionized water, and drying at room temperature for 6-9 hours to complete the loading of CeCo2Fe 16 O 27 crystals on the surface of the Ni(PDA)2(PANI)2 coordination polymer, and finally obtaining the foam copper-based composite material (foam copper-based [Ni(PDA)2(PANI)2] coordination polymer loaded with CeCo2Fe 16 O 27 crystals), and a schematic diagram of the microstructure thereof is shown in Figure 2 .

[0044] The preferred embodiments of the present application are described below.

[0045] Example 1

[0046] The preferred embodiment 1 of the present application provides a preparation method of a foam copper-based composite material with photothermal effect, comprising the following steps:

[0047] Step [1] loading nickel atom modified polydopamine / aniline composite organic matter on the surface of foamed copper matrix, specifically comprising the following operations:

[0048] a1. adding p-aminobenzoic acid, m-phenylenediamine, dopamine hydrochloride, aminoacetic acid and sodium hydroxide into deionized water to form a base solution, wherein the amount of p-aminobenzoic acid, m-phenylenediamine, dopamine hydrochloride, aminoacetic acid and sodium hydroxide added in the base solution is 40 g, 100 g, 90 g, 20 g and 120 g per liter respectively; adding azobis (isobutyronitrile) into ethanol to form an additive solution, wherein the amount of azobis (isobutyronitrile) added in the additive solution is 50 g per liter; mixing the base solution and the additive solution in a volume ratio of 10:3 to form a reaction solution, immersing foamed copper sample into the reaction solution (the weight of foamed copper immersed in the reaction solution is 210 g per liter), heating to 125℃ and reacting for 5 hours, then taking out the sample and washing with deionized water to obtain foamed copper loaded with polydopamine / aniline composite organic matter on the surface, denoted as intermediate A;

[0049] a2. adding bis (1, 5-cyclooctadiene) nickel into tetrahydrofuran to form a modification solution, wherein the amount of bis (1, 5-cyclooctadiene) nickel added in the modification solution is 20 g per liter; immersing the intermediate A into the modification solution (the weight of intermediate A immersed in the modification solution is 60 g per liter), soaking at room temperature for 5 hours, then taking out the sample and washing with deionized water, and drying at room temperature for 10 hours to obtain foamed copper loaded with nickel atom modified polydopamine / aniline composite organic matter on the surface, denoted as intermediate B.

[0050] Step [2] converting the nickel atom modified polydopamine / aniline composite organic matter on the surface of foamed copper matrix into Ni (PDA) 2 (PANI) 2 coordination polymer, specifically comprising the following operations:

[0051] b1. adding nickel sulfate, N-methylaniline, sodium pyrosulfite and dopamine hydrochloride into deionized water to form a coordination polymer construction solution (the concentration of nickel sulfate, sodium pyrosulfite and dopamine hydrochloride in the polymer construction solution is 80 g / L, 26 g / L and 60 g / L respectively; the amount of N-methylaniline added in the polymer construction solution is 40 ml per liter);

[0052] b2. immersing the intermediate B into the coordination polymer construction solution (the weight of intermediate B immersed in the coordination polymer construction solution is 160 g per liter), heating to 80℃ in a water bath, reacting for 13 hours, drying at room temperature for 7 hours to obtain foamed copper loaded with Ni (PDA) 2 (PANI) 2 coordination polymer on the surface, denoted as intermediate C.

[0053] Step [3] loading CeCo2Fe 16O 27 crystals, specifically comprising the following operations:

[0054] c1. adding ceric sulfate, hexamine cobalt chloride, ferric chloride, and concentrated nitric acid with a mass fraction of 68% into deionized water to form a crystallization solution (the concentration of ceric sulfate in the crystallization solution is 70 g / L, the concentration of ferric chloride is 140 g / L, the mass fraction of nitric acid is 5%, and the amount of hexamine cobalt chloride added in the crystallization solution is 110 g per liter);

[0055] c2. immersing the intermediate C in the crystallization solution (the weight of the intermediate C immersed in the crystallization solution is 230 g per liter), heating the water bath to 60°C, reacting for 13 hours, washing with deionized water, and drying at room temperature for 8 hours to complete the CeCo2Fe 16 O 27 crystals on the surface of the Ni(PDA)2(PANI)2 coordination polymer, and finally obtaining the foam copper-based composite material (foam copper-based [Ni(PDA)2(PANI)2] coordination polymer loaded CeCo2Fe 16 O 27 crystals), which is referred to as Example 1.

[0056] Comparative Example 1

[0057] The comparative example 1 provides a preparation method of a foam copper-based composite material, comprising the following steps:

[0058] Step [1] loading nickel atom modified polydopamine / aniline composite organic matter on the surface of a foam copper substrate, specifically comprising the following operations:

[0059] a1. adding p-aminobenzoic acid, m-phenylenediamine, dopamine hydrochloride, aminoacetic acid, and sodium hydroxide into deionized water to form a base solution, wherein the amount of p-aminobenzoic acid added in the base solution is 25 g per liter, the amount of m-phenylenediamine added is 80 g per liter, the amount of dopamine hydrochloride added is 85 g per liter, the amount of aminoacetic acid added is 15 g per liter, and the amount of sodium hydroxide added is 20 g per liter; adding azobisisheptyl nitrile into ethanol to form an additive solution, wherein the amount of azobisisheptyl nitrile added in the additive solution is 40 g per liter; mixing the base solution and the additive solution in a volume ratio of 9:2 to form a reaction solution, immersing a foam copper sample in the reaction solution (the weight of the foam copper immersed in the reaction solution is 180 g per liter), heating to 120°C, and reacting for 4 hours, then washing the sample with deionized water to obtain foam copper loaded with polydopamine / aniline composite organic matter, which is referred to as intermediate A;

[0060] a2. Bis(1,5-cyclooctadiene)nickel was added to tetrahydrofuran to form a modification solution, wherein the amount of bis(1,5-cyclooctadiene)nickel added to the modification solution was 15 g per liter of the modification solution; the intermediate A was immersed in the modification solution (the weight of the intermediate A immersed in the modification solution was 55 g per liter of the modification solution), and immersed at room temperature for 4 hours. After the sample was taken out, it was washed with deionized water and dried at room temperature for 9 hours to obtain a foam copper with a surface loaded with nickel atom modified polydopamine / aniline composite organic matter, denoted as intermediate B.

[0061] Step [2] converting the nickel atom modified polydopamine / aniline composite organic matter on the surface of the foam copper substrate into a Ni(PDA)2(PANI)2 coordination polymer, specifically including the following operations:

[0062] b1. Nickel sulfate, N-methylaniline, sodium pyrosulfite and dopamine hydrochloride were added to deionized water to form a coordination polymer construction solution (the concentration of nickel sulfate in the polymer construction solution was 60 g / L, the concentration of sodium pyrosulfite was 25 g / L, and the concentration of dopamine hydrochloride was 50 g / L; the amount of N-methylaniline added to the polymer construction solution was 20 ml per liter of the polymer construction solution).

[0063] b2. The intermediate B was immersed in the coordination polymer construction solution (the weight of the intermediate B immersed in the coordination polymer construction solution was 150 g per liter of the coordination polymer construction solution), and heated to 60°C in a water bath for 12 hours. After drying at room temperature for 6 hours, a foam copper with a surface loaded with a Ni(PDA)2(PANI)2 coordination polymer was obtained, denoted as Comparative Example 1.

[0064] Comparative Example 2

[0065] The present comparative example 2 provides a method for preparing a foam copper-based composite material, comprising the following steps:

[0066] Step [1] loading a nickel atom modified polydopamine / aniline composite organic matter on the surface of a foam copper substrate, specifically including the following operations:

[0067] a1. Add p-aminobenzoic acid, m-phenylenediamine, dopamine hydrochloride, aminoacetic acid and sodium hydroxide into deionized water to form a base solution, wherein the amount of p-aminobenzoic acid, m-phenylenediamine, dopamine hydrochloride, aminoacetic acid and sodium hydroxide added in the base solution is 40 g, 90 g, 85 g, 20 g and 25 g per liter of the base solution respectively; add azobis (isobutyronitrile) into ethanol to form an additive solution, wherein the amount of azobis (isobutyronitrile) added in the additive solution is 40 g per liter of the additive solution; mix the base solution and the additive solution in a volume ratio of 11:2 to form a reaction solution, immerse the foam copper sample into the reaction solution (the weight of the foam copper immersed in the reaction solution is 180 g per liter of the reaction solution), heat to 120°C, react for 4 hours, take out the sample and wash with deionized water to obtain foam copper loaded with polydopamine / aniline composite organic matter on the surface, denoted as intermediate A;

[0068] a2. Add bis (1, 5-cyclooctadiene) nickel into tetrahydrofuran to form a modification solution, wherein the amount of bis (1, 5-cyclooctadiene) nickel added in the modification solution is 20 g per liter of the modification solution; immerse the intermediate A into the modification solution (the weight of the intermediate A immersed in the modification solution is 55 g per liter of the modification solution), soak at room temperature for 6 hours, take out the sample and wash with deionized water, and dry at room temperature for 9 hours to obtain foam copper loaded with nickel atom modified polydopamine / aniline composite organic matter on the surface, denoted as intermediate B.

[0069] Step [2] load CeCo2Fe 16 O 27 crystals on the surface of nickel atom modified polydopamine / aniline composite organic matter, specifically including the following operations:

[0070] c1. Add ceric sulfate, hexammine cobalt chloride, ferric chloride and concentrated nitric acid with a mass fraction of 68% into deionized water to form a crystallization solution (the concentration of ceric sulfate in the crystallization solution is 70 g / L, the concentration of ferric chloride is 135 g / L, the mass fraction of nitric acid is 4%, and the amount of hexammine cobalt chloride added in the crystallization solution is 90 g per liter of the crystallization solution);

[0071] c2. Immerse the intermediate B into the crystallization solution (the weight of the intermediate B immersed in the crystallization solution is 230 g per liter of the crystallization solution), heat to 60°C in a water bath, react for 12 hours, wash with deionized water, and dry at room temperature for 7 hours to complete the loading of CeCo2Fe 16 O 27 crystals on the surface of nickel atom modified polydopamine / aniline composite organic matter, and finally obtain the foam copper-based composite material (foam copper-based nickel atom modified polydopamine / aniline composite organic matter loaded with CeCo2Fe 16 O 27 crystals), denoted as Comparative Example 2.

[0072] To analyze the photothermal effect and the performance of activated peracetic acid in degrading metronidazole-containing wastewater in Examples 1, 1, and 2, metronidazole was added to deionized water to form simulated metronidazole-containing wastewater with a metronidazole concentration of 10 mg / L. 100 ml of the simulated metronidazole-containing wastewater was poured into each beaker, and 50 g of each of Examples 1, 1, and 2 were added to the beaker. A 15% peracetic acid solution was added to the simulated metronidazole-containing wastewater to bring the peracetic acid concentration to 1 mmol / L. Comparative Examples 1, 2, and 1 were irradiated with visible light at a wavelength of 550 nm using a 300W xenon lamp for 30 minutes. The photothermal effect temperature of Examples 1, 1, and 2 during the degradation of metronidazole-containing wastewater by activated peracetic acid under photothermal irradiation was measured using an infrared thermal imager (results are shown in Figure 1). Figure 3 As shown in the figure, the concentration of metronidazole in the process of photo-activated peracetic acid degradation of metronidazole-containing wastewater was detected and measured by high performance liquid chromatography (with a control group without light exposure set up simultaneously), and the metronidazole degradation rate of the corresponding process was calculated (results are shown in the figure). Figure 4 (As shown). By Figure 3 It can be seen that the temperature of Example 1 reached 78°C after 30 minutes of simulated sunlight exposure, significantly higher than the 52°C of Comparative Example 1 and the 44°C of Comparative Example 2. Figure 4 It can be seen that, under light conditions, the photothermal effect of Example 1 can effectively activate peracetic acid and thus degrade metronidazole-containing wastewater, with a metronidazole degradation rate of 93%, which is much higher than the 62% of Comparative Example 1 and the 54% of Comparative Example 2. Meanwhile, under the condition of no light and only the addition of 1 mmol / L peracetic acid, the metronidazole degradation rates of Example 1, Comparative Example 1, and Comparative Example 2 are only 47%, 31%, and 24%, respectively. Under the condition of no light and no peracetic acid, Example 1, Comparative Example 1, and Comparative Example 2 have basically no degradation effect on metronidazole-containing wastewater.

[0073] In summary, the copper-based foam composite material prepared according to the present invention has excellent photothermal effect and can efficiently activate peracetic acid to degrade metronidazole wastewater.

[0074] To illustrate this further in detail, three more embodiments are provided below.

[0075] Example 2

[0076] Preferred embodiment 2 of the present invention provides a method for preparing a foamed copper-based composite material with photothermal effect, comprising the following steps:

[0077] Step [1] involves loading nickel atoms onto the surface of a copper foam substrate to modify a polydopamine / aniline composite organic compound, specifically including the following operations:

[0078] a1. Add p-aminobenzoic acid, m-phenylenediamine, dopamine hydrochloride, aminoacetic acid and sodium hydroxide into deionized water to form a base solution, wherein the amount of p-aminobenzoic acid, m-phenylenediamine, dopamine hydrochloride, aminoacetic acid and sodium hydroxide added in the base solution is 20 g, 110 g, 80 g, 10 g and 30 g per liter of the base solution respectively; add azobis (isobutyronitrile) into ethanol to form an additive solution, wherein the amount of azobis (isobutyronitrile) added in the additive solution is 30 g per liter of the additive solution; mix the base solution and the additive solution in a volume ratio of 11:2 to form a reaction solution, immerse the foam copper sample into the reaction solution (the weight of the foam copper immersed in the reaction solution is 170 g per liter of the reaction solution), heat to 110°C, react for 5 hours, take out the sample and wash with deionized water to obtain foam copper loaded with polydopamine / aniline composite organic matter on the surface, denoted as intermediate A;

[0079] a2. Add bis (1, 5-cyclooctadiene) nickel into tetrahydrofuran to form a modification solution, wherein the amount of bis (1, 5-cyclooctadiene) nickel added in the modification solution is 10 g per liter of the modification solution; immerse the intermediate A into the modification solution (the weight of the intermediate A immersed in the modification solution is 50 g per liter of the modification solution), soak at room temperature for 4 hours, take out the sample and wash with deionized water, and dry at room temperature for 8 hours to obtain foam copper loaded with nickel atom modified polydopamine / aniline composite organic matter on the surface, denoted as intermediate B.

[0080] Step [2] converts the nickel atom modified polydopamine / aniline composite organic matter on the surface of the foam copper matrix into Ni (PDA) 2 (PANI) 2 coordination polymer, specifically including the following operations:

[0081] b1. Add nickel sulfate, N-methylaniline, sodium pyrosulfite and dopamine hydrochloride into deionized water to form a coordination polymer construction solution (the concentration of nickel sulfate, sodium pyrosulfite and dopamine hydrochloride in the polymer construction solution is 50 g / L, 30 g / L and 40 g / L respectively; the amount of N-methylaniline added in the polymer construction solution is 10 ml per liter of the polymer construction solution);

[0082] b2. Immerse the intermediate B into the coordination polymer construction solution (the weight of the intermediate B immersed in the coordination polymer construction solution is 140 g per liter of the coordination polymer construction solution), heat in a water bath to 90°C, react for 10 hours, dry at room temperature for 6 hours to obtain foam copper loaded with Ni (PDA) 2 (PANI) 2 coordination polymer on the surface, denoted as intermediate C.

[0083] Step [3] loads CeCo2Fe 16 O 27 crystal on the surface of the Ni (PDA) 2 (PANI) 2 coordination polymer, specifically including the following operations:

[0084] c1. adding ceric sulfate, hexammine cobalt chloride, ferric chloride, and concentrated nitric acid with a mass fraction of 68% into deionized water to form a crystallization solution (the concentration of ceric sulfate in the crystallization solution is 50 g / L, the concentration of ferric chloride is 150 g / L, the mass fraction of nitric acid is 3%, and the amount of hexammine cobalt chloride added in the crystallization solution is 80 g per liter);

[0085] c2. immersing the intermediate C in the crystallization solution (the weight of the intermediate C immersed in the crystallization solution is 220 g per liter), heating to 70°C in a water bath, reacting for 10 hours, washing with deionized water, and drying at room temperature for 9 hours to obtain the CeCo2Fe 16 O 27 crystals on the surface of the Ni(PDA)2(PANI)2 coordination polymer, and finally obtaining the foam copper-based composite material (foam copper-based [Ni(PDA)2(PANI)2] coordination polymer loaded CeCo2Fe 16 O 27 crystals).

[0086] Example 3

[0087] The preferred embodiment 3 of the present application provides a preparation method of a foam copper-based composite material with a photothermal effect, comprising the following steps:

[0088] Step [1] loading nickel atom modified polydopamine / aniline composite organic matter on the surface of a foam copper substrate, specifically comprising the following operations:

[0089] a1. adding p-aminobenzoic acid, m-phenylenediamine, dopamine hydrochloride, aminoacetic acid, and sodium hydroxide into deionized water to form a base solution, wherein the amount of p-aminobenzoic acid added in the base solution is 50 g per liter, the amount of m-phenylenediamine added is 70 g per liter, the amount of dopamine hydrochloride added is 100 g per liter, the amount of aminoacetic acid added is 25 g per liter, and the amount of sodium hydroxide added is 15 g per liter; adding azobisisheptyl nitrile into ethanol to form an additive solution, wherein the amount of azobisisheptyl nitrile added in the additive solution is 60 g per liter; mixing the base solution and the additive solution in a volume ratio of 9:2 to form a reaction solution, immersing a foam copper sample in the reaction solution (the weight of the foam copper immersed in the reaction solution is 220 g per liter), heating to 130°C, and reacting for 3 hours; after taking out the sample, washing with deionized water to obtain foam copper with polydopamine / aniline composite organic matter loaded on the surface, denoted as intermediate A;

[0090] a2. Bis(1,5-cyclooctadiene)nickel is added to tetrahydrofuran to form a modification solution, wherein the amount of bis(1,5-cyclooctadiene)nickel added to the modification solution is 25 g per liter of the modification solution; the intermediate A is immersed in the modification solution (the weight of the intermediate A immersed in the modification solution is 70 g per liter of the modification solution), impregnated at room temperature for 6 hours, washed with deionized water after the sample is taken out, and dried at room temperature for 12 hours to obtain a foam copper with a nickel atom modified polydopamine / aniline composite organic material loaded on the surface, denoted as intermediate B.

[0091] Step [2] converting the nickel atom modified polydopamine / aniline composite organic material on the surface of the foam copper matrix into a Ni(PDA)2(PANI)2 coordination polymer, specifically comprising the following operations:

[0092] b1. Nickel sulfate, N-methylaniline, sodium pyrosulfite and dopamine hydrochloride are added to deionized water to form a coordination polymer construction solution (the concentration of nickel sulfate in the polymer construction solution is 80 g / L, the concentration of sodium pyrosulfite is 20 g / L, the concentration of dopamine hydrochloride is 70 g / L; the amount of N-methylaniline added to the polymer construction solution is 50 ml per liter of the polymer construction solution);

[0093] b2. The intermediate B is immersed in the coordination polymer construction solution (the weight of the intermediate B immersed in the coordination polymer construction solution is 170 g per liter of the coordination polymer construction solution), heated to 50°C in a water bath, reacted for 14 hours, dried at room temperature for 8 hours, and a foam copper with a Ni(PDA)2(PANI)2 coordination polymer loaded on the surface is obtained, denoted as intermediate C.

[0094] Step [3] loading CeCo2Fe 16 O 27 crystals on the surface of the Ni(PDA)2(PANI)2 coordination polymer, specifically comprising the following operations:

[0095] c1. Cerium sulfate, hexammine cobalt trichloride, iron chloride and concentrated nitric acid with a mass fraction of 68% are added to deionized water to form a crystallization solution (the concentration of cerium sulfate in the crystallization solution is 80 g / L, the concentration of iron chloride is 130 g / L, the mass fraction of nitric acid is 6%, and the amount of hexammine cobalt trichloride added to the crystallization solution is 120 g per liter of the crystallization solution);

[0096] c2. The intermediate C is immersed in the crystallization solution (the weight of the intermediate C immersed in the crystallization solution is 240 g per liter of the crystallization solution), heated to 50°C in a water bath, reacted for 16 hours, washed with deionized water, and dried at room temperature for 6 hours to complete the loading of CeCo2Fe 16 O 27 crystals on the surface of the Ni(PDA)2(PANI)2 coordination polymer, and finally obtain the foam copper-based composite material (foam copper-based [Ni(PDA)2(PANI)2] coordination polymer loaded with CeCo2Fe16 O 27 crystal).

[0097] Example 4

[0098] The preferred embodiment 4 of the present application provides a preparation method of a foam copper-based composite material with photothermal effect, comprising the following steps:

[0099] Step [1] loading nickel atom modified polydopamine / aniline composite organic matter on the surface of the foam copper matrix, specifically comprising the following operations:

[0100] a1. adding p-aminobenzoic acid, m-phenylenediamine, dopamine hydrochloride, aminoacetic acid and sodium hydroxide into deionized water to form a base solution, wherein the amount of p-aminobenzoic acid added in each liter of the base solution is 35g, the amount of m-phenylenediamine added is 90g, the amount of dopamine hydrochloride added is 90g, the amount of aminoacetic acid added is 16g, and the amount of sodium hydroxide added is 23g; adding azobisisoheptane cyanide into ethanol to form an additive solution, wherein the amount of azobisisoheptane cyanide added in each liter of the additive solution is 45g; mixing the base solution and the additive solution in a volume ratio of 10:3 to form a reaction solution, immersing the foam copper sample into the reaction solution (the weight of the foam copper immersed in each liter of the reaction solution is 195g), heating to 120℃, and reacting for 4 hours; after taking out the sample, washing with deionized water to obtain foam copper loaded with polydopamine / aniline composite organic matter on the surface, denoted as intermediate A;

[0101] a2. adding bis(1,5-cyclooctadiene)nickel into tetrahydrofuran to form a modification solution, wherein the amount of bis(1,5-cyclooctadiene)nickel added in each liter of the modification solution is 19g; immersing the intermediate A into the modification solution (the weight of the intermediate A immersed in each liter of the modification solution is 60g), and dipping at room temperature for 5 hours; after taking out the sample, washing with deionized water and drying at room temperature for 10 hours to obtain foam copper loaded with nickel atom modified polydopamine / aniline composite organic matter on the surface, denoted as intermediate B.

[0102] Step [2] converting the nickel atom modified polydopamine / aniline composite organic matter on the surface of the foam copper matrix into Ni(PDA)2(PANI)2 coordination polymer, specifically comprising the following operations:

[0103] b1. adding nickel sulfate, N-methylaniline, sodium pyrosulfite and dopamine hydrochloride into deionized water to form a coordination polymer construction solution (the concentration of nickel sulfate in the polymer construction solution is 65g / L, the concentration of sodium pyrosulfite is 25g / L, and the concentration of dopamine hydrochloride is 55g / L; the amount of N-methylaniline added in each liter of the polymer construction solution is 30ml);

[0104] b2. The intermediate B is immersed in the coordination polymer building solution (155 g of the intermediate B is immersed in every liter of the coordination polymer building solution), heated to 70 DEG C in a water bath for 12 hours, and dried at room temperature for 7 hours to obtain the foam copper with the Ni(PDA)2(PANI)2 coordination polymer loaded on the surface, denoted as intermediate C.

[0105] Step [3] loading CeCo2Fe 16 O 27 crystals, specifically comprising the following operations:

[0106] c1. Cerium sulfate, hexammine cobalt chloride, ferric chloride, and concentrated nitric acid with a mass fraction of 68% are added to deionized water to form a crystallization solution (the concentration of cerium sulfate in the crystallization solution is 65 g / L, the concentration of ferric chloride is 140 g / L, the mass fraction of nitric acid is 5%, and 100 g of hexammine cobalt chloride is added to every liter of the crystallization solution);

[0107] c2. The intermediate C is immersed in the crystallization solution (230 g of the intermediate C is immersed in every liter of the crystallization solution), heated to 60 DEG C in a water bath for 13 hours, washed with deionized water, and dried at room temperature for 9 hours to complete the loading of the CeCo2Fe 16 O 27 crystals on the surface of the Ni(PDA)2(PANI)2 coordination polymer, and finally obtain the foam copper-based composite material (foam copper-based [Ni(PDA)2(PANI)2] coordination polymer loaded with CeCo2Fe 16 O 27 crystals).

[0108] The above merely describes preferred embodiments of the present application, and it should be understood that the above description of the embodiments is only used to help understand the method of the present application and its core idea, and is not used to limit the protection scope of the present application, and any modification, equivalent replacement, etc. within the idea and principles of the present application should be included in the protection scope of the present application.

Claims

1. A method for preparing a foamed copper-based composite material having a photothermal effect, characterized by, The method comprises the following steps: Step [1] loading nickel atom modified polydopamine / aniline composite organic matter on the surface of the foamed copper matrix, specifically comprising the following operations: a1. adding p-aminobenzoic acid, m-phenylenediamine, dopamine hydrochloride, aminoacetic acid and sodium hydroxide into deionized water to form a base solution; adding azobis (isobutyronitrile) into ethanol to form an additive solution; mixing the base solution and the additive solution in a certain proportion to form a reaction solution; immersing the foamed copper sample into the reaction solution, heating to 110-130 DEG C, and reacting for 3-5 hours; after taking out the sample, washing with deionized water to obtain foamed copper loaded with polydopamine / aniline composite organic matter on the surface, denoted as intermediate A; a2. adding bis (1, 5-cyclooctadiene) nickel into tetrahydrofuran to form a modification solution; immersing the intermediate A into the modification solution, soaking at room temperature for 4-6 hours; after taking out the sample, washing with deionized water and drying at room temperature for 8-12 hours to obtain foamed copper loaded with nickel atom modified polydopamine / aniline composite organic matter on the surface, denoted as intermediate B; Step [2] converting the nickel atom modified polydopamine / aniline composite organic matter on the surface of the foamed copper matrix into Ni (PDA) 2 (PANI) 2 coordination polymer, specifically comprising the following operations: b1. adding nickel sulfate, N-methylaniline, sodium pyrosulfite and dopamine hydrochloride into deionized water to form a coordination polymer construction solution; b2. immersing the intermediate B into the coordination polymer construction solution, heating in a water bath to 50-90 DEG C, reacting for 10-14 hours, and drying at room temperature for 6-8 hours to obtain foamed copper loaded with Ni (PDA) 2 (PANI) 2 coordination polymer on the surface, denoted as intermediate C; Step [3] CeCo2Fe loading on the surface of Ni(PDA)2(PANI)2 coordination polymer 16 O 27 crystals, including the following operations: c1. adding ceric sulfate, hexammine cobalt chloride, ferric chloride and concentrated nitric acid with a mass fraction of 68% into deionized water to form a crystallization solution; c2. The intermediate C is immersed in the crystallization solution, heated to 50-70°C in a water bath, and reacted for 10-16 hours. After washing with deionized water, the product is dried at room temperature for 6-9 hours. The CeCo2Fe 16 O 27 The crystals are loaded on the surface of the Ni(PDA)2(PANI)2 coordination polymer, and finally the copper-based foam composite is obtained.

2. The method of claim 1, wherein the method further comprises: In step a1, the amount of p-aminobenzoic acid added in the base solution is 20-50 g per liter, the amount of m-phenylenediamine added is 70-110 g per liter, the amount of dopamine hydrochloride added is 80-100 g per liter, the amount of aminoacetic acid added is 10-25 g per liter, the amount of sodium hydroxide added is 15-30 g per liter, the amount of azobis (isobutyronitrile) added in the additive solution is 30-60 g per liter, and the volume ratio of the base solution to the additive solution in the reaction solution is 9-11: 2-3; the weight of the foamed copper immersed in the reaction solution is 170-220 g per liter. ​ 3. The method of claim 1, wherein the method further comprises: applying a copper layer on the substrate; and applying a copper layer on the copper layer. In step a2, the amount of bis (1, 5-cyclooctadiene) nickel added in the modification solution is 10-25 g per liter, and the weight of the intermediate A immersed in the modification solution is 50-70 g per liter.

4. The method of claim 1, wherein the method further comprises: In step b1, the concentration of nickel sulfate in the polymer construction solution is 50-80 g / L, the concentration of sodium pyrosulfite is 20-30 g / L, and the concentration of dopamine hydrochloride is 40-70 g / L; the amount of N-methylaniline added in the polymer construction solution is 10-50 ml per liter. ​ 5. The method of claim 1, wherein the method further comprises: In step b2, the weight of the intermediate B immersed in the coordination polymer construction solution is 140-170 g per liter. ​ 6. The method of claim 1, wherein the method further comprises: In step c1, the cerium sulfate concentration in the crystallization solution is 50-80 g / L, the ferric chloride concentration is 130-150 g / L, the mass fraction of nitric acid is 3-6%, and the amount of hexammine cobalt chloride added to each liter of the crystallization solution is 80-120 g. ​ 7. The method of claim 1, wherein the method further comprises: In step c2, the weight of the intermediate C immersed in each liter of the crystallization solution is 220-240 g. ​

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