Preparation method of foam copper-based organic catalytic material for treating chloride ion wastewater

Abstract

The application provides a preparation method of a foamed copper-based organic catalytic material for treating chloride ion wastewater, comprising the following steps in sequence: step [1], forming a cobalt aminoacetate [Co(gly)3] organic compound layer on the surface of a foamed copper base; step [2], converting the cobalt aminoacetate [Co(gly)3] on the surface of the foamed copper base into cobalt samarium aminoacetate [CoSm(gly)6] through a samarium Sm replacement reaction; and step [3], converting the cobalt samarium aminoacetate [CoSm(gly)6] on the surface of the foamed copper base into samarium acetylacetone ethylenediamine / cobalt aminoacetate [Sm(acac)2(en)][Co(gly)3], and finally obtaining the foamed copper-based organic catalytic material. The catalytic material prepared according to the application has the advantages of high chloride ion removal rate, excellent corrosion resistance and long-term stability.

Description

Technical Field

[0001] This invention relates to the field of organic compound catalytic materials, and in particular to a method for preparing a copper-based organic catalytic material for treating chloride ion wastewater. Background Technology

[0002] Industries such as metal smelting, papermaking, power electronics, ore mining, power plant desulfurization wastewater, pharmaceutical preparation, and electroplating all generate large amounts of wastewater with high concentrations of chloride ions. Chloride ions are stable structures with eight electrons in their outermost shell, representing the most stable state of chlorine. Microorganisms cannot transform or degrade chloride ions. However, wastewater with high concentrations of chloride ions must be treated to remove chloride ions and meet relevant standards before it can be discharged. Otherwise, it will not only cause soil salinization and water pollution but also seriously threaten the survival of organisms.

[0003] Electrochemical chloride ion catalytic oxidation chlorine release technology involves electrolyzing chloride-containing wastewater under an applied electric field. Chloride ions undergo an oxidation reaction at the electrolytic anode, releasing chlorine gas and thus removing high concentrations of chloride ions from the wastewater. This technology requires simple equipment and processes, and the generated chlorine gas can be sealed and recovered to produce various chemical products such as chlorides and synthetic fibers. It represents a potentially effective approach for treating high-concentration chloride ion wastewater.

[0004] However, the electrochemical chloride ion catalytic oxidation of chlorine not only faces competition from the electrocatalytic oxygen evolution reaction (OER), but also suffers from severe corrosion in the chloride ion environment. This results in unsatisfactory chloride ion removal efficiency in existing electrochemical chloride ion catalytic oxidation technologies, and the corrosion resistance and long-term stability of electrode materials for the electrocatalytic chlorine evolution reaction fall far short of practical requirements. Therefore, there is an urgent need to develop a catalytic material for electrocatalytic chlorine evolution that possesses high chloride ion removal efficiency, excellent corrosion resistance, and long-term stability. Summary of the Invention

[0005] To overcome the shortcomings of existing technologies, this invention provides a method for preparing a foamed copper-based organic catalytic material for treating chloride ion wastewater. The catalytic material prepared by this method has advantages such as high chloride ion removal rate, excellent corrosion resistance, and long-term stability.

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

[0007] This invention provides a method for preparing a foamed copper-based organic catalytic material for treating chloride ion wastewater, comprising the following steps performed in sequence:

[0008] Step [1]: Form a layer of cobalt glycine [Co(gly)3] organic compound on the surface of the copper foam substrate;

[0009] Step [2] converts cobalt gammaacetate [Co(gly)3] on the surface of the copper foam matrix into samarium cobalt gammaacetate [CoSm(gly)6] through a samarium Sm substitution reaction;

[0010] Step [3] converts the cobalt samarium glyamine [CoSm(gly)6] on the surface of the copper foam matrix into samarium acetylacetone / cobalt glyamine [Sm(acac)2(en)][Co(gly)3], and finally obtains the copper foam-based organic catalytic material.

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

[0012] a1. Mix diethyl ether and deionized water to form a base solution; add glycine, thioacetic acid, dimethyl sulfoxide, benzoyl peroxide and cobalt nitrate to the base solution and mix evenly to form a synthesis solution; immerse foamed copper metal in the synthesis solution and react at room temperature for 2-3 hours; remove the foamed copper metal and wash it with deionized water to obtain intermediate A;

[0013] a2. Add glycine, oxalic acid, sodium perborate and cobalt nitrate to deionized water and mix evenly to form a crystallizing solution. Immerse intermediate A in the crystallizing solution and soak at 45-70℃ for 3-7 hours to obtain foamed copper with a cobalt glycine [Co(gly)3] organic compound layer on the surface, denoted as intermediate B.

[0014] Preferably, in step a1, the volume ratio of diethyl ether to deionized water in the base solution is 4-5:1-3; the concentration of glycine in the synthesis solution is 70g / L-110g / L, the concentration of thioacetic acid is 15mL / L-35mL / L, the concentration of dimethyl sulfoxide is 50mL / L-65mL / L, the concentration of benzoyl peroxide is 40g / L-90g / L, and the concentration of cobalt nitrate is 90g / L-140g / L; and the weight of copper foam immersed in each liter of the synthesis solution is 220-270g.

[0015] Preferably, in step a2, the concentration of glycine in the crystallization solution is 200 g / L-270 g / L, the concentration of oxalic acid is 50 g / L-90 g / L, the concentration of sodium perborate is 80 g / L-110 g / L, and the concentration of cobalt nitrate is 270 g / L-330 g / L; the weight of intermediate A immersed in each liter of the crystallization solution is 150-200 g.

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

[0017] b1. Add glycine, samarium sulfate, oxalic acid, and sodium perborate to deionized water and mix thoroughly to form the first conversion solution;

[0018] b2. Immerse the intermediate B in the first conversion solution and react at room temperature for 2 to 5 hours to convert cobalt glycine [Co(gly)3] on the surface of the copper foam substrate into samarium cobalt glycine [CoSm(gly)6] to obtain intermediate C.

[0019] Preferably, in step b1, the concentration of glycine in the first conversion solution is 120 g / L-180 g / L, the concentration of samarium sulfate is 100 g / L-130 g / L, the concentration of oxalic acid is 40 g / L-90 g / L, and the concentration of sodium perborate is 50 g / L-70 g / L.

[0020] Preferably, in step b2, the weight of intermediate B immersed in each liter of the first conversion solution is 170-230g.

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

[0022] c1. Dissolve zinc acetylacetonate in methanol to form additive solution A; add ethylenediamine, acetylacetonate, samarium sulfate and phenylalanine to deionized water to form additive solution B; mix additive solution A and additive solution B to form a second conversion solution;

[0023] c2. Immerse the intermediate C in the second conversion solution and react it in a reactor at 80-110°C for 2-4 hours to finally obtain the foamed copper-based organic catalytic material for electrocatalytic chlorine evolution.

[0024] Preferably, in step c1, the concentration of zinc acetylacetone in additive solution A is 210 g / L-250 g / L; the concentration of ethylenediamine in additive solution B is 170 mL / L-200 mL / L, the concentration of acetylacetone is 40 mL / L-60 mL / L, the concentration of samarium sulfate is 80 g / L-120 g / L, and the concentration of phenylalanine is 30 g / L-70 g / L; the volume ratio between additive solution A and additive solution B in the second conversion solution is 1-3:3-5.

[0025] Preferably, in step c2, the weight of intermediate C immersed in each liter of the second conversion solution is 240-270g.

[0026] The positive effects of this invention are as follows: The foamed copper-based organic catalytic material (sammonium acetylacetone ethylenediamine / cobalt glyamine [Sm(acac)2(en)][Co(gly)3]) prepared by the method described in this invention is a samarium-cobalt cluster organic compound. Its structural features are as follows: cobalt atoms and samarium atoms are located at the center of the base and top faces of a regular triangular prism. The cobalt atoms are bonded to the three glyamine ions located at the vertices of the equilateral triangle on the base face of the regular triangular prism. The samarium atoms are bonded to the two acetylacetone ions and one ethylenediamine ion located at the vertices of the equilateral triangle on the top face of the regular triangular prism. At the same time, the samarium atoms of acetylacetone ethylenediamine samarium [Sm(acac)2(en)] and the cobalt atoms of glyamine [Co(gly)3] are connected by metallic bonds. In this invention, the cobalt ions of cobalt glyacetate [Co(gly)3] can reduce the potential barrier for the electrochemical oxidation of chloride ions to chlorine atoms, while the samarium ions of samarium acetylacetone ethylenediamine [Sm(acac)2(en)] not only increase the active sites for chloride evolution but also increase the electron transfer rate in the electrocatalytic process, significantly accelerating the kinetics of electrocatalytic chloride evolution. Simultaneously, the ethylenediamine group of acetylacetone can inhibit the intermediate products MOOH and MOH in the electrochemical oxidation of oxygen, effectively improving the catalytic activity and selectivity of electrocatalytic chloride evolution. Furthermore, the chelate bonding structure of samarium acetylacetone ethylenediamine / cobalt glyacetate [Sm(acac)2(en)][Co(gly)3] exhibits high stability, effectively improving the corrosion resistance of the catalytic material. In summary, the foamed copper-based organic catalytic material prepared according to this invention possesses high chloride ion removal rate, excellent corrosion resistance, and long-term stability. Attached Figure Description

[0027] Figure 1 This is a schematic diagram of the preparation process of the copper-based foamed organic catalytic material described in this invention;

[0028] Figure 2 This is a schematic diagram of the structure of cobalt glyamine [Co(gly)3] as described in this invention;

[0029] Figure 3 This is a schematic diagram of the structure of samarium cobalt aminoacetate [CoSm(gly)6] as described in this invention;

[0030] Figure 4 This is a schematic diagram of the structure of acetylacetone ethylenediamine samarium / cobalt aminoacetate [Sm(acac)2(en)][Co(gly)3] as described in this invention;

[0031] Figure 5a This is a comparison chart of chloride ion removal rates under different applied voltages in Example 1 of the present invention;

[0032] Figure 5b This is a comparison chart of chloride ion removal rates under different applied voltages in Comparative Example 1 of this invention;

[0033] Figure 5c This is a comparison chart of chloride ion removal rates under different applied voltages in Comparative Example 2 of this invention;

[0034] Figure 6 This is a graph showing the relationship between the number of electrocatalytic chlorine evolution experiments and the chloride ion removal rate in Examples 1, 1, and 2 of this invention.

[0035] Figure 7 The average corrosion weight loss rate of Examples 1, Comparative Example 1, and Comparative Example 2 of the present invention under different electrocatalytic times. Detailed Implementation

[0036] Reference Figure 1 This invention provides a method for preparing a foamed copper-based organic catalytic material for treating chloride ion wastewater, comprising the following steps performed in sequence:

[0037] Step [1] involves forming a cobalt glycine [Co(gly)3] organic compound layer on the surface of the copper foam substrate, specifically including the following operations:

[0038] a1. Mix diethyl ether and deionized water in a volume ratio of 4-5:1-3 to form a base solution; add glycine, thioacetic acid, dimethyl sulfoxide, benzoyl peroxide, and cobalt nitrate to the base solution and mix thoroughly to form a synthesis solution with glycine concentration of 70 g / L-110 g / L, thioacetic acid concentration of 15 mL / L-35 mL / L, dimethyl sulfoxide concentration of 50 mL / L-65 mL / L, benzoyl peroxide concentration of 40 g / L-90 g / L, and cobalt nitrate concentration of 90 g / L-140 g / L; immerse foamed copper metal in the synthesis solution (the weight of foamed copper immersed in each liter of the synthesis solution is 220-270 g), react at room temperature for 2-3 hours, remove the foamed copper metal, wash with deionized water to obtain intermediate A.

[0039] a2. Glycoacetic acid, oxalic acid, sodium perborate, and cobalt nitrate are added to deionized water and mixed evenly to form a crystallization solution with a glycoacetic acid concentration of 200 g / L-270 g / L, an oxalic acid concentration of 50 g / L-90 g / L, a sodium perborate concentration of 80 g / L-110 g / L, and a cobalt nitrate concentration of 270 g / L-330 g / L. Intermediate A is immersed in the crystallization solution (150-200 g of intermediate A is immersed in each liter of the crystallization solution) and soaked at a temperature of 45-70°C for 3-7 hours to complete the crystallization process of cobalt glycoacetic acid [Co(gly)3] organic compound, obtaining foam copper with a cobalt glycoacetic acid [Co(gly)3] organic compound layer on the surface, denoted as intermediate B; wherein, the structure of the cobalt glycoacetic acid [Co(gly)3] is as follows. Figure 2 As shown.

[0040] Step [2] involves converting cobalt glycerate [Co(gly)3] on the surface of the copper foam substrate into samarium cobalt glycerate [CoSm(gly)6] via a samarium Sm substitution reaction, specifically including the following operations:

[0041] b1. Add glycine, samarium sulfate, oxalic acid, and sodium perborate to deionized water and mix thoroughly to form a first conversion solution with glycine concentration of 120g / L-180g / L, samarium sulfate concentration of 100g / L-130g / L, oxalic acid concentration of 40g / L-90g / L, and sodium perborate concentration of 50g / L-70g / L;

[0042] b2. Immerse the intermediate B in the first conversion solution (the weight of intermediate B immersed in each liter of the first conversion solution is 170-230 g), and react at room temperature for 2-5 hours to convert cobalt gammaacetate [Co(gly)3] on the surface of the copper foam substrate into samarium gammaacetate [CoSm(gly)6], to obtain intermediate C; wherein the structure of samarium gammaacetate [CoSm(gly)6] is as follows: Figure 3 As shown.

[0043] Step [3] converts the cobalt samarium glyamine [CoSm(gly)6] on the surface of the copper foam substrate into samarium acetylacetone ethylenediamine / cobalt glyamine [Sm(acac)2(en)][Co(gly)3], and finally obtains the copper foam-based organic catalytic material. The specific steps include the following:

[0044] c1. Dissolve zinc acetylacetonate in methanol to form additive solution A with a zinc acetylacetonate concentration of 210 g / L-250 g / L; add ethylenediamine, acetylacetonate, samarium sulfate, and phenylalanine to deionized water to form additive solution B with an ethylenediamine concentration of 170 mL / L-200 mL / L, an acetylacetonate concentration of 40 mL / L-60 mL / L, a samarium sulfate concentration of 80 g / L-120 g / L, and a phenylalanine concentration of 30 g / L-70 g / L; mix additive solution A and additive solution B in a volume ratio of 1-3:3-5 to form a second conversion solution;

[0045] c2. Immerse the intermediate C in the second conversion solution (the weight of intermediate C immersed in each liter of the second conversion solution is 240-270 g), and react in a reactor at 80-110°C for 2-4 hours to convert the samarium cobalt aminoacetate [CoSm(gly)6] on the surface of the copper foam substrate into samarium acetylacetone ethylenediamine / cobalt aminoacetate [Sm(acac)2(en)][Co(gly)3], the structure of which is as follows: Figure 4As shown, the final product obtained is a copper-based organic catalyst foam (copper-based acetylacetone ethylenediamine samarium / cobalt aminoacetate) used for electrocatalytic chlorine evolution.

[0046] The preferred embodiments of the present invention will be described below by way of example.

[0047] Example 1

[0048] Preferred embodiment 1 of the present invention provides a method for preparing a foamed copper-based organic catalytic material for treating chloride ion wastewater, comprising the following steps performed in sequence:

[0049] Step [1] involves forming a cobalt glycine [Co(gly)3] organic compound layer on the surface of the copper foam substrate, specifically including the following operations:

[0050] a1. Mix diethyl ether and deionized water in a volume ratio of 4:3 to form a base solution; add glycine, thioacetic acid, dimethyl sulfoxide, benzoyl peroxide, and cobalt nitrate to the base solution and mix thoroughly to form a synthesis solution with glycine concentration of 80 g / L, thioacetic acid concentration of 30 mL / L, dimethyl sulfoxide concentration of 60 mL / L, benzoyl peroxide concentration of 80 g / L, and cobalt nitrate concentration of 130 g / L; immerse foamed copper metal in the synthesis solution (the weight of foamed copper immersed in each liter of the synthesis solution is 240 g), react at room temperature for 3 hours, remove the foamed copper metal, wash with deionized water to obtain intermediate A;

[0051] a2. Glycoacetic acid, oxalic acid, sodium perborate, and cobalt nitrate are added to deionized water and mixed evenly to form a crystallization solution with a glycoacetic acid concentration of 230 g / L, an oxalic acid concentration of 60 g / L, a sodium perborate concentration of 100 g / L, and a cobalt nitrate concentration of 320 g / L. Intermediate A is immersed in the crystallization solution (the weight of intermediate A immersed in each liter of the crystallization solution is 190 g) and soaked at 60°C for 4 hours to obtain foam copper with a cobalt glycoacetic acid [Co(gly)3] organic compound layer on the surface, which is denoted as intermediate B.

[0052] Step [2] involves converting cobalt glycerate [Co(gly)3] on the surface of the copper foam substrate into samarium cobalt glycerate [CoSm(gly)6] via a samarium Sm substitution reaction, specifically including the following operations:

[0053] b1. Add glycine, samarium sulfate, oxalic acid, and sodium perborate to deionized water and mix thoroughly to form a first conversion solution with glycine concentration of 130 g / L, samarium sulfate concentration of 120 g / L, oxalic acid concentration of 50 g / L, and sodium perborate concentration of 60 g / L.

[0054] b2. Immerse the intermediate B in the first conversion solution (the weight of intermediate B immersed in each liter of the first conversion solution is 220g) and react at room temperature for 4 hours to convert cobalt glycerate [Co(gly)3] on the surface of the copper foam substrate into samarium cobalt glycerate [CoSm(gly)6] to obtain intermediate C.

[0055] Step [3] converts the cobalt samarium glyamine [CoSm(gly)6] on the surface of the copper foam substrate into samarium acetylacetone ethylenediamine / cobalt glyamine [Sm(acac)2(en)][Co(gly)3], and finally obtains the copper foam-based organic catalytic material. The specific steps include the following:

[0056] c1. Dissolve zinc acetylacetonate in methanol to form additive solution A with a zinc acetylacetonate concentration of 240 g / L; add ethylenediamine, acetylacetonate, samarium sulfate, and phenylalanine to deionized water to form additive solution B with an ethylenediamine concentration of 175 mL / L, an acetylacetonate concentration of 50 mL / L, a samarium sulfate concentration of 90 g / L, and a phenylalanine concentration of 60 g / L; mix additive solution A and additive solution B at a volume ratio of 2:5 to form a second conversion solution;

[0057] c2. The intermediate C is immersed in the second conversion solution (the weight of intermediate C immersed in each liter of the second conversion solution is 260g), and reacted in a reactor at 100°C for 3 hours to convert the cobalt samarium gammaacetate [CoSm(gly)6] on the surface of the copper foam matrix into samarium acetylacetone ethylenediamine / cobalt gammaacetate [Sm(acac)2(en)][Co(gly)3], and finally obtains the copper foam-based organic catalytic material for electrocatalytic chlorine evolution (referred to as Example 1).

[0058] Comparative Example 1

[0059] Comparative Example 1 provides a method for preparing a foamed copper-based samarium acetylacetone / cobalt glycine organic material, comprising the following steps performed in sequence:

[0060] Step [1] involves forming a cobalt glycine [Co(gly)3] organic compound layer on the surface of the copper foam substrate, specifically including the following operations:

[0061] a1. Mix diethyl ether and deionized water in a volume ratio of 4:1 to form a base solution; add glycine, thioacetic acid, dimethyl sulfoxide, benzoyl peroxide, and cobalt nitrate to the base solution and mix thoroughly to form a synthesis solution with glycine concentration of 80 g / L, thioacetic acid concentration of 25 mL / L, dimethyl sulfoxide concentration of 50 mL / L, benzoyl peroxide concentration of 50 g / L, and cobalt nitrate concentration of 100 g / L; immerse foamed copper metal in the synthesis solution (the weight of foamed copper immersed in each liter of the synthesis solution is 240 g), react at room temperature for 2 hours, remove the foamed copper metal, wash with deionized water to obtain intermediate A;

[0062] a2. Glycoacetic acid, oxalic acid, sodium perborate, and cobalt nitrate are added to deionized water and mixed evenly to form a crystallization solution with a glycoacetic acid concentration of 220 g / L, an oxalic acid concentration of 60 g / L, a sodium perborate concentration of 90 g / L, and a cobalt nitrate concentration of 280 g / L. Intermediate A is immersed in the crystallization solution (160 g of intermediate A is immersed in each liter of the crystallization solution) and soaked at 50°C for 4 hours to obtain foamed copper with a cobalt glycoacetic acid [Co(gly)3] organic compound layer on the surface, which is denoted as intermediate B.

[0063] Step [2] involves converting cobalt glycerate [Co(gly)3] on the surface of the copper foam substrate into samarium cobalt glycerate [CoSm(gly)6] via a samarium Sm substitution reaction, specifically including the following operations:

[0064] b1. Add glycine, samarium sulfate, oxalic acid, and sodium perborate to deionized water and mix thoroughly to form a first conversion solution with glycine concentration of 130 g / L, samarium sulfate concentration of 110 g / L, oxalic acid concentration of 50 g / L, and sodium perborate concentration of 60 g / L.

[0065] b2. Immerse the intermediate B in the first conversion solution (the weight of intermediate B immersed in each liter of the first conversion solution is 200g) and react at room temperature for 3 hours to convert cobalt glycerate [Co(gly)3] on the surface of the copper foam substrate into samarium cobalt glycerate [CoSm(gly)6] to obtain intermediate C.

[0066] Step [3] converts the samarium cobalt glycerate [CoSm(gly)6] on the surface of the copper foam substrate into samarium acetylacetonate / cobalt glycerate [Sm(acac)3)][Co(gly)3], specifically including the following operations:

[0067] c1. Dissolve zinc acetylacetonate in methanol to form additive solution A with a zinc acetylacetonate concentration of 230 g / L; add acetylacetonate, samarium sulfate, and phenylalanine to deionized water to form additive solution B with a acetylacetonate concentration of 50 mL / L, a samarium sulfate concentration of 90 g / L, and a phenylalanine concentration of 40 g / L; mix additive solution A and additive solution B at a volume ratio of 1:3 to form a second conversion solution;

[0068] c2. The intermediate C is immersed in the second conversion solution (the weight of intermediate C immersed in each liter of the second conversion solution is 250g), and reacted in a reactor at 90°C for 3 hours to convert the samarium cobalt acetone [CoSm(gly)6] on the surface of the copper foam matrix into samarium acetylacetonate / cobalt glyacetone [Sm(acac)3][Co(gly)3], and finally obtain the copper foam-based samarium acetylacetonate / cobalt glyacetone organic material (referred to as Comparative Example 1).

[0069] Comparative Example 2

[0070] Comparative Example 2 provides a method for preparing a foamed copper-based ethylenediamine samarium / cobalt aminoacetate organic material, comprising the following steps performed in sequence:

[0071] Step [1] involves forming a cobalt glycine [Co(gly)3] organic compound layer on the surface of the copper foam substrate, specifically including the following operations:

[0072] a1. Mix diethyl ether and deionized water in a volume ratio of 5:2 to form a base solution; add glycine, thioacetic acid, dimethyl sulfoxide, benzoyl peroxide, and cobalt nitrate to the base solution and mix thoroughly to form a synthesis solution with glycine concentration of 100 g / L, thioacetic acid concentration of 30 mL / L, dimethyl sulfoxide concentration of 60 mL / L, benzoyl peroxide concentration of 70 g / L, and cobalt nitrate concentration of 130 g / L; immerse foamed copper metal in the synthesis solution (the weight of foamed copper immersed in each liter of the synthesis solution is 260 g), react at room temperature for 3 hours, remove the foamed copper metal, wash with deionized water to obtain intermediate A;

[0073] a2. Glycoacetic acid, oxalic acid, sodium perborate, and cobalt nitrate are added to deionized water and mixed evenly to form a crystallization solution with a glycoacetic acid concentration of 260 g / L, an oxalic acid concentration of 80 g / L, a sodium perborate concentration of 90 g / L, and a cobalt nitrate concentration of 300 g / L. Intermediate A is immersed in the crystallization solution (the weight of intermediate A immersed in each liter of the crystallization solution is 190 g) and soaked at 60°C for 6 hours to obtain foam copper with a cobalt glycoacetic acid [Co(gly)3] organic compound layer on the surface, which is denoted as intermediate B.

[0074] Step [2] involves converting cobalt glycerate [Co(gly)3] on the surface of the copper foam substrate into samarium cobalt glycerate [CoSm(gly)6] via a samarium Sm substitution reaction, specifically including the following operations:

[0075] b1. Add glycine, samarium sulfate, oxalic acid, and sodium perborate to deionized water and mix thoroughly to form a first conversion solution with glycine concentration of 170 g / L, samarium sulfate concentration of 120 g / L, oxalic acid concentration of 80 g / L, and sodium perborate concentration of 60 g / L.

[0076] b2. Immerse the intermediate B in the first conversion solution (the weight of intermediate B immersed in each liter of the first conversion solution is 200g) and react at room temperature for 4 hours to convert cobalt glycerate [Co(gly)3] on the surface of the copper foam substrate into samarium cobalt glycerate [CoSm(gly)6] to obtain intermediate C.

[0077] Step [3] converts the samarium cobalt glyamine [CoSm(gly)6] on the surface of the copper foam substrate into samarium ethylenediamine / cobalt glyamine [Sm(en)3][Co(gly)3], specifically including the following operations:

[0078] c1. Ethylenediamine, samarium sulfate and phenylalanine are added to deionized water to form a second conversion solution with ethylenediamine concentration of 190 mL / L, samarium sulfate concentration of 110 g / L and phenylalanine concentration of 60 g / L;

[0079] c2. The intermediate C is immersed in the second conversion solution (the weight of intermediate C immersed in each liter of the second conversion solution is 260g), and reacted in a reactor at 100°C for 4 hours to convert the samarium cobalt aminoacetate [CoSm(gly)6] on the surface of the copper foam matrix into ethylenediamine samarium / cobalt aminoacetate [Sm(en)3][Co(gly)3], and finally obtain the copper foam-based ethylenediamine samarium / cobalt aminoacetate organic material (referred to as Comparative Example 2).

[0080] To analyze the chloride ion removal rate, corrosion resistance, and long-term stability of the electrocatalytic oxidation of chloride ions in Examples 1, Comparative Examples 1, and 2, a NaCl solution with a Cl- concentration of 1.5 g / L was used to simulate high-concentration chloride ion wastewater. Electrochemical catalytic experiments were conducted using Examples 1, Comparative Examples 1, and 2 as the anode electrode, a carbon rod as the auxiliary electrode, and a saturated calomel electrode as the reference electrode. The closed electrolytic cell was connected to a conduit containing a 5% sodium hydroxide solution to absorb the chlorine gas generated by the electrocatalytic oxidation of chloride ions.

[0081] The chloride ion removal rate after specific experiments was quantitatively measured using silver nitrate titration. Specifically, under experimental conditions of applied voltages of 3V, 4V, and 5V, and an electrocatalytic reaction time of 200 minutes, the chloride ion removal rates of Example 1, Comparative Example 1, and Comparative Example 2 were measured. - Removal rate experimental results are as follows Figure 5a As shown in -c, Example 1 achieved a chloride ion removal rate of over 80% when the applied voltage was 4V and 5V, while the chloride ion removal rates of Comparative Example 1 and Comparative Example 2 were both less than 15%.

[0082] Under the condition of applying an external voltage of 4V for 200 minutes, the results of the number of electrocatalytic chlorine evolution experiments and the Cl- removal rate in Example 1, Comparative Example 1, and Comparative Example 2 are as follows: Figure 6 As shown, when Example 1 was used as the catalytic electrode material for electrocatalytic chlorine evolution for the 40th consecutive time, its chloride ion removal rate remained at 80%, while the chloride ion removal rates of Comparative Example 1 and Comparative Example 2 were both below 5% after the 30th consecutive test.

[0083] The average corrosion weight loss rates of Examples 1, Comparative Example 1, and Comparative Example 2 during the electrocatalytic chlorine evolution experiment under the conditions of an applied 4V voltage for 72 hours and 144 hours are as follows: Figure 7 As shown, the average corrosion weight loss rate in Example 1 was only 4.7 μg / cm³. 2 ·day (72 hours) and 4.9μg / cm 2 • day (144 hours), the corresponding average corrosion weight loss rate of Comparative Example 1 is 98 μg / cm³. 2 ·day (72 hours) and 113μg / cm 2 • day (144 hours), the corresponding average corrosion weight loss rate of Comparative Example 2 was as high as 132 μg / cm. 2 ·day (72 hours) and 164μg / cm 2 ·day (144 hours).

[0084] Based on the above experimental results, the foamed copper-based acetylacetone ethylenediamine samarium / cobalt aminoacetate organic catalytic material prepared according to the present invention has the characteristics of high chloride ion removal rate, excellent corrosion resistance and long-term stability.

[0085] To illustrate this further in detail, three more embodiments are provided below.

[0086] Example 2

[0087] Preferred embodiment 2 of the present invention provides a method for preparing a foamed copper-based organic catalytic material for treating chloride ion wastewater, comprising the following steps performed in sequence:

[0088] Step [1] involves forming a cobalt glycine [Co(gly)3] organic compound layer on the surface of the copper foam substrate, specifically including the following operations:

[0089] a1. Mix diethyl ether and deionized water in a volume ratio of 4:1 to form a base solution; add glycine, thioacetic acid, dimethyl sulfoxide, benzoyl peroxide, and cobalt nitrate to the base solution and mix thoroughly to form a synthesis solution with glycine concentration of 70 g / L, thioacetic acid concentration of 15 mL / L, dimethyl sulfoxide concentration of 50 mL / L, benzoyl peroxide concentration of 90 g / L, and cobalt nitrate concentration of 140 g / L; immerse foamed copper metal in the synthesis solution (the weight of foamed copper immersed in each liter of the synthesis solution is 220 g), react at room temperature for 2 hours, remove the foamed copper metal, wash with deionized water to obtain intermediate A;

[0090] a2. Glycoacetic acid, oxalic acid, sodium perborate, and cobalt nitrate are added to deionized water and mixed evenly to form a crystallization solution with a glycoacetic acid concentration of 270 g / L, an oxalic acid concentration of 90 g / L, a sodium perborate concentration of 80 g / L, and a cobalt nitrate concentration of 330 g / L. Intermediate A is immersed in the crystallization solution (200 g of intermediate A is immersed in each liter of the crystallization solution) and soaked at 45°C for 7 hours to obtain foamed copper with a cobalt glycoacetic acid [Co(gly)3] organic compound layer on the surface, which is denoted as intermediate B.

[0091] Step [2] involves converting cobalt glycerate [Co(gly)3] on the surface of the copper foam substrate into samarium cobalt glycerate [CoSm(gly)6] via a samarium Sm substitution reaction, specifically including the following operations:

[0092] b1. Add glycine, samarium sulfate, oxalic acid, and sodium perborate to deionized water and mix thoroughly to form a first conversion solution with glycine concentration of 180 g / L, samarium sulfate concentration of 130 g / L, oxalic acid concentration of 90 g / L, and sodium perborate concentration of 50 g / L.

[0093] b2. Immerse the intermediate B in the first conversion solution (the weight of intermediate B immersed in each liter of the first conversion solution is 170g) and react at room temperature for 2 hours to convert cobalt glyacetate [Co(gly)3] on the surface of the copper foam substrate into samarium cobalt glyacetate [CoSm(gly)6] to obtain intermediate C.

[0094] Step [3] converts the cobalt samarium glyamine [CoSm(gly)6] on the surface of the copper foam substrate into samarium acetylacetone ethylenediamine / cobalt glyamine [Sm(acac)2(en)][Co(gly)3], and finally obtains the copper foam-based organic catalytic material. The specific steps include the following:

[0095] c1. Dissolve zinc acetylacetonate in methanol to form additive solution A with a zinc acetylacetonate concentration of 210 g / L; add ethylenediamine, acetylacetonate, samarium sulfate, and phenylalanine to deionized water to form additive solution B with an ethylenediamine concentration of 200 mL / L, an acetylacetonate concentration of 60 mL / L, a samarium sulfate concentration of 82 g / L, and a phenylalanine concentration of 30 g / L; mix additive solution A and additive solution B in a volume ratio of 3:5 to form a second conversion solution;

[0096] c2. The intermediate C is immersed in the second conversion solution (the weight of intermediate C immersed in each liter of the second conversion solution is 241g), and reacted in a reactor at 110°C for 2 hours to convert the cobalt samarium gammaacetate [CoSm(gly)6] on the surface of the copper foam matrix into samarium acetylacetone ethylenediamine / cobalt gammaacetate [Sm(acac)2(en)][Co(gly)3], and finally obtains the copper foam-based organic catalytic material for electrocatalytic chlorine evolution.

[0097] Example 3

[0098] Preferred embodiment 3 of the present invention provides a method for preparing a foamed copper-based organic catalytic material for treating chloride ion wastewater, comprising the following steps performed in sequence:

[0099] Step [1] involves forming a cobalt glycine [Co(gly)3] organic compound layer on the surface of the copper foam substrate, specifically including the following operations:

[0100] a1. Mix diethyl ether and deionized water in a volume ratio of 5:3 to form a base solution; add glycine, thioacetic acid, dimethyl sulfoxide, benzoyl peroxide, and cobalt nitrate to the base solution and mix thoroughly to form a synthesis solution with glycine concentration of 110 g / L, thioacetic acid concentration of 35 mL / L, dimethyl sulfoxide concentration of 63 mL / L, benzoyl peroxide concentration of 40 g / L, and cobalt nitrate concentration of 90 g / L; immerse foamed copper metal in the synthesis solution (the weight of foamed copper immersed in each liter of the synthesis solution is 270 g), react at room temperature for 3 hours, remove the foamed copper metal, wash with deionized water to obtain intermediate A;

[0101] a2. Glycoacetic acid, oxalic acid, sodium perborate, and cobalt nitrate are added to deionized water and mixed evenly to form a crystallization solution with a glycoacetic acid concentration of 200 g / L, an oxalic acid concentration of 50 g / L, a sodium perborate concentration of 110 g / L, and a cobalt nitrate concentration of 270 g / L. Intermediate A is immersed in the crystallization solution (150 g of intermediate A is immersed in each liter of the crystallization solution) and soaked at 70°C for 3 hours to obtain foam copper with a cobalt glycoacetic acid [Co(gly)3] organic compound layer on the surface, which is denoted as intermediate B.

[0102] Step [2] involves converting cobalt glycerate [Co(gly)3] on the surface of the copper foam substrate into samarium cobalt glycerate [CoSm(gly)6] via a samarium Sm substitution reaction, specifically including the following operations:

[0103] b1. Add glycine, samarium sulfate, oxalic acid, and sodium perborate to deionized water and mix thoroughly to form a first conversion solution with glycine concentration of 120 g / L, samarium sulfate concentration of 100 g / L, oxalic acid concentration of 40 g / L, and sodium perborate concentration of 69 g / L.

[0104] b2. Immerse the intermediate B in the first conversion solution (the weight of intermediate B immersed in each liter of the first conversion solution is 230g) and react at room temperature for 5 hours to convert cobalt glycerate [Co(gly)3] on the surface of the copper foam substrate into samarium cobalt glycerate [CoSm(gly)6] to obtain intermediate C.

[0105] Step [3] converts the cobalt samarium glyamine [CoSm(gly)6] on the surface of the copper foam substrate into samarium acetylacetone ethylenediamine / cobalt glyamine [Sm(acac)2(en)][Co(gly)3], and finally obtains the copper foam-based organic catalytic material. The specific steps include the following:

[0106] c1. Dissolve zinc acetylacetonate in methanol to form additive solution A with a zinc acetylacetonate concentration of 245 g / L; add ethylenediamine, acetylacetonate, samarium sulfate, and phenylalanine to deionized water to form additive solution B with an ethylenediamine concentration of 170 mL / L, an acetylacetonate concentration of 40 mL / L, a samarium sulfate concentration of 120 g / L, and a phenylalanine concentration of 70 g / L; mix additive solution A and additive solution B at a volume ratio of 1:3 to form a second conversion solution;

[0107] c2. The intermediate C is immersed in the second conversion solution (the weight of intermediate C immersed in each liter of the second conversion solution is 270g), and reacted in a reactor at 80°C for 4 hours to convert the cobalt samarium gammaacetate [CoSm(gly)6] on the surface of the copper foam matrix into samarium acetylacetone ethylenediamine / cobalt gammaacetate [Sm(acac)2(en)][Co(gly)3], and finally obtains the copper foam-based organic catalytic material for electrocatalytic chlorine evolution.

[0108] Example 4

[0109] Preferred embodiment 4 of the present invention provides a method for preparing a foamed copper-based organic catalytic material for treating chloride ion wastewater, comprising the following steps performed in sequence:

[0110] Step [1] involves forming a cobalt glycine [Co(gly)3] organic compound layer on the surface of the copper foam substrate, specifically including the following operations:

[0111] a1. Mix diethyl ether and deionized water in a volume ratio of 3:2 to form a base solution; add glycine, thioacetic acid, dimethyl sulfoxide, benzoyl peroxide, and cobalt nitrate to the base solution and mix thoroughly to form a synthesis solution with glycine concentration of 90 g / L, thioacetic acid concentration of 25 mL / L, dimethyl sulfoxide concentration of 60 mL / L, benzoyl peroxide concentration of 60 g / L, and cobalt nitrate concentration of 115 g / L; immerse foamed copper metal in the synthesis solution (the weight of foamed copper immersed in each liter of the synthesis solution is 245 g), react at room temperature for 2.5 hours, remove the foamed copper metal, wash with deionized water to obtain intermediate A;

[0112] a2. Glycoacetic acid, oxalic acid, sodium perborate, and cobalt nitrate are added to deionized water and mixed evenly to form a crystallization solution with a glycoacetic acid concentration of 235 g / L, an oxalic acid concentration of 70 g / L, a sodium perborate concentration of 95 g / L, and a cobalt nitrate concentration of 300 g / L. Intermediate A is immersed in the crystallization solution (the weight of intermediate A immersed in each liter of the crystallization solution is 175 g) and soaked at 55°C for 5 hours to obtain foamed copper with a cobalt glycoacetic acid [Co(gly)3] organic compound layer on the surface, which is denoted as intermediate B.

[0113] Step [2] involves converting cobalt glycerate [Co(gly)3] on the surface of the copper foam substrate into samarium cobalt glycerate [CoSm(gly)6] via a samarium Sm substitution reaction, specifically including the following operations:

[0114] b1. Add glycine, samarium sulfate, oxalic acid, and sodium perborate to deionized water and mix thoroughly to form a first conversion solution with glycine concentration of 150 g / L, samarium sulfate concentration of 115 g / L, oxalic acid concentration of 65 g / L, and sodium perborate concentration of 60 g / L.

[0115] b2. Immerse the intermediate B in the first conversion solution (the weight of intermediate B immersed in each liter of the first conversion solution is 200g) and react at room temperature for 3.5 hours to convert cobalt glyacetate [Co(gly)3] on the surface of the copper foam substrate into samarium cobalt glyacetate [CoSm(gly)6] to obtain intermediate C.

[0116] Step [3] converts the cobalt samarium glyamine [CoSm(gly)6] on the surface of the copper foam substrate into samarium acetylacetone ethylenediamine / cobalt glyamine [Sm(acac)2(en)][Co(gly)3], and finally obtains the copper foam-based organic catalytic material. The specific steps include the following:

[0117] c1. Dissolve zinc acetylacetonate in methanol to form additive solution A with a zinc acetylacetonate concentration of 230 g / L; add ethylenediamine, acetylacetonate, samarium sulfate, and phenylalanine to deionized water to form additive solution B with an ethylenediamine concentration of 185 mL / L, an acetylacetonate concentration of 50 mL / L, a samarium sulfate concentration of 100 g / L, and a phenylalanine concentration of 50 g / L; mix additive solution A and additive solution B in a volume ratio of 2:3 to form a second conversion solution;

[0118] c2. The intermediate C is immersed in the second conversion solution (the weight of intermediate C immersed in each liter of the second conversion solution is 255g), and reacted in a reactor at 95°C for 3 hours to convert the cobalt samarium aminoacetate [CoSm(gly)6] on the surface of the copper foam matrix into samarium acetylacetone ethylenediamine / cobalt aminoacetate [Sm(acac)2(en)][Co(gly)3], and finally obtains the copper foam-based organic catalytic material for electrocatalytic chlorine evolution.

[0119] The above description is only a preferred embodiment of the present invention. It should be understood that the above description of the embodiments is only for the purpose of helping to understand the method and core idea of ​​the present invention, and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, etc. made within the idea and principle of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a foamed copper-based organic catalytic material for treating chloride ion wastewater, characterized in that, It includes the following steps performed in sequence: Step [1]: Form a layer of cobalt glycine [Co(gly)3] organic compound on the surface of the copper foam substrate; Step [2] The cobalt glyamine [Co(gly)3] on the surface of the copper foam matrix is ​​converted into samarium cobalt glyamine [CoSm(gly)6] by samarium Sm substitution reaction; Step [3]: The cobalt samarium glyamine [CoSm (gly)6] on the surface of the copper foam substrate is converted into samarium acetylacetone diamine / cobalt glyamine [Sm(acac)2(en)][Co(gly)3], and finally the copper foam-based organic catalytic material is obtained.

2. The method for preparing a foamed copper-based organic catalytic material for treating chloride ion wastewater according to claim 1, characterized in that, The steps [1] specifically include the following operations: a1. Mix diethyl ether and deionized water to form a base solution; add glycine, thioacetic acid, dimethyl sulfoxide, benzoyl peroxide and cobalt nitrate to the base solution and mix evenly to form a synthesis solution; immerse foamed copper metal in the synthesis solution and react at room temperature for 2-3 hours; remove the foamed copper metal and wash it with deionized water to obtain intermediate A; a2. Add glycine, oxalic acid, sodium perborate and cobalt nitrate to deionized water and mix evenly to form a crystallizing solution. Immerse intermediate A in the crystallizing solution and soak at 45-70℃ for 3-7 hours to obtain foamed copper with a cobalt glycine [Co(gly)3] organic compound layer on the surface, denoted as intermediate B.

3. The method for preparing a foamed copper-based organic catalytic material for treating chloride ion wastewater according to claim 2, characterized in that: In step a1, the volume ratio of diethyl ether to deionized water in the base solution is 4~5:1~3; the concentration of glycine in the synthesis solution is 70g / L-110g / L, the concentration of thioacetic acid is 15mL / L-35mL / L, the concentration of dimethyl sulfoxide is 50mL / L-65mL / L, the concentration of benzoyl peroxide is 40g / L-90g / L, and the concentration of cobalt nitrate is 90g / L-140g / L; the weight of copper foam immersed in each liter of the synthesis solution is 220-270g.

4. The method for preparing a foamed copper-based organic catalytic material for treating chloride ion wastewater according to claim 2, characterized in that... The concentration of glycine in the crystallization solution in step a2 is 200 g / L-270 g / L, the concentration of oxalic acid is 50 g / L-90 g / L, the concentration of sodium perborate is 80 g / L-110 g / L, and the concentration of cobalt nitrate is 270 g / L-330 g / L; the weight of intermediate A immersed in each liter of the crystallization solution is 150-200 g.

5. The method for preparing a foamed copper-based organic catalytic material for treating chloride ion wastewater according to claim 2, characterized in that, The steps [2] specifically include the following operations: b1. Add glycine, samarium sulfate, oxalic acid, and sodium perborate to deionized water and mix thoroughly to form the first conversion solution; b2. Immerse the intermediate B in the first conversion solution and react at room temperature for 2-5 hours to convert cobalt glycine [Co(gly)3] on the surface of the copper foam substrate into samarium cobalt glycine [CoSm(gly)6], to obtain intermediate C.

6. The method for preparing a foamed copper-based organic catalytic material for treating chloride ion wastewater according to claim 5, characterized in that... In step b1, the concentration of glycine in the first conversion solution is 120 g / L-180 g / L, the concentration of samarium sulfate is 100 g / L-130 g / L, the concentration of oxalic acid is 40 g / L-90 g / L, and the concentration of sodium perborate is 50 g / L-70 g / L.

7. The method for preparing a foamed copper-based organic catalytic material for treating chloride ion wastewater according to claim 5, characterized in that... In step b2, the weight of intermediate B immersed in each liter of the first conversion solution is 170-230g.

8. The method for preparing a foamed copper-based organic catalytic material for treating chloride ion wastewater according to claim 5, characterized in that, The specific steps [3] include the following operations: c1. Dissolve zinc acetylacetonate in methanol to form additive solution A; add ethylenediamine, acetylacetonate, samarium sulfate and phenylalanine to deionized water to form additive solution B; mix additive solution A and additive solution B to form a second conversion solution; c2. Immerse the intermediate C into the second conversion solution and react it in a reactor at 80-110°C for 2-4 hours to finally obtain a foamed copper-based organic catalyst material for electrocatalytic chlorine evolution.

9. The method for preparing a foamed copper-based organic catalytic material for treating chloride ion wastewater according to claim 8, characterized in that... In step c1, the concentration of zinc acetylacetone in additive solution A is 210 g / L-250 g / L; the concentration of ethylenediamine in additive solution B is 170 mL / L-200 mL / L, the concentration of acetylacetone is 40 mL / L-60 mL / L, the concentration of samarium sulfate is 80 g / L-120 g / L, and the concentration of phenylalanine is 30 g / L-70 g / L; the volume ratio between additive solution A and additive solution B in the second conversion solution is 1~3:3~5.

10. The method for preparing a foamed copper-based organic catalytic material for treating chloride ion wastewater according to claim 8, characterized in that... In step c2, the weight of intermediate C immersed in each liter of the second conversion solution is 240-270g.

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