Preparation method of visible light catalytic material for degrading atenolol-containing sewage

Abstract

The invention provides a preparation method of a visible light catalytic material for degrading atenolol-containing sewage. The preparation method comprises the following steps: (1) loading a [Ni (C10H10O2) 2] coordination compound on the surface of a foam iron matrix; (2) converting the [Ni (C10H10O2) 2] coordination compound loaded on the surface of the iron powder matrix into a [Ni (C16H6O8) 2 (C10H10O2)] n coordination polymer; and step [3], embedding GaMo4S8 nanoparticles on the surface of the [Ni (C16H6O8) 2 (C10H10O2)] n coordination polymer. The visible light catalytic material prepared by the method disclosed by the invention has efficient and excellent atenolol photocatalytic degradation performance.

Description

Technical Field

[0001] The invention relates to the technical field of atenolol-containing sewage treatment, in particular to a method for preparing a visible light catalytic material for degrading atenolol-containing sewage. Background Art

[0002] Atenolol is a β-adrenergic receptor blocking drug that can occupy the β1 receptors present in the heart. By blocking the action of β1 receptors, it can reduce the heart rate, reduce the effect of catechol on the myocardium, and inhibit myocardial contraction; it can also occupy the β2 receptors located in the bronchial smooth muscle, which can effectively inhibit the expansion of the bronchi. Atenolol is widely used in the treatment of diseases such as hypertension, angina pectoris, coronary heart disease, heart failure, and lowering heart rate. With the development of the global economy, changes in lifestyles, and changes in the aging of the population in developed and emerging countries, the number of users and the amount of use of atenolol are increasing. The oral absorption rate of atenolol is 50%, and it is mainly excreted in urine through the prototype. Since atenolol is soluble in water, it has become a detectable pollutant in various environmental water bodies. Atenolol wastewater poses a serious threat to humans and the environment. Atenolol wastewater entering the human body will directly damage the human cardiovascular system, nervous system, digestive system and respiratory system, and has significant biological toxicity to the earth's environment. Therefore, the effective treatment of atenolol wastewater has reached a stage that cannot be delayed.

[0003] Visible light catalytic degradation of organic pollutants is a technology that generates photogenerated electrons and holes in the process of visible light irradiation of photocatalytic degradation materials. The photogenerated electrons and holes can produce active free radicals, thereby achieving the degradation of organic pollutants under the condition of making full use of solar energy. Obviously, visible light catalytic degradation technology is a green and effective treatment process for treating atenolol wastewater. However, there is currently a lack of catalytic materials with excellent and efficient visible light catalytic degradation of atenolol-containing wastewater and corresponding preparation methods and processes, which has become a bottleneck restricting the development of visible light catalytic degradation technology for atenolol wastewater. Summary of the invention

[0004] In order to overcome the shortcomings of the prior art, the present invention provides a method for preparing a visible light catalytic material for degrading wastewater containing atenolol. The visible light catalytic material prepared by the method has high efficiency and excellent atenolol photocatalytic degradation performance.

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

[0006] The present invention provides a method for preparing a visible light catalytic material for degrading atenolol-containing sewage, comprising the following steps:

[0007] Step [1] Loading [Ni(C 10 H 10 O2)2] coordination compounds;

[0008] Step [2]: Loading [Ni(C 10 H 10 O2)2] coordination compound is converted to [Ni(C 16 H6O8)2(C 10 H 10 O2)] n Coordination polymers;

[0009] Step [3] In [Ni(C 16 H6O8)2(C 10 H 10 O2)] n GaMo4S8 nanoparticles are embedded on the surface of the coordination polymer.

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

[0011] a1. Nickel chloride hexammine, nickel sulfate and trimethylamine oxide are added to deionized water and mixed to form an inorganic base liquid; benzoyl acetone is added to ethanol and mixed to form an organic additive liquid; a certain amount of the organic additive liquid is added to the inorganic base liquid and mixed to form a loading liquid;

[0012] a2. The foamed iron sample was immersed in the loading liquid and used as the cathode, the stainless steel plate was used as the anode, and electrophoretic deposition was performed at a constant voltage of 30V to 60V at room temperature for 20 to 30 minutes to obtain a surface loaded with [Ni(C 10 H 10 O2)2] coordination compound, recorded as intermediate A.

[0013] Preferably, in step a1, the concentration of hexaamminenickel chloride in the inorganic base liquid is 5-20 g / L, the concentration of nickel sulfate is 120-160 g / L, and the concentration of trimethylamine oxide is 40-80 g / L; the concentration of benzoylacetone in the organic additive liquid is 60 g / L-90 g / L; and the volume ratio between the organic additive liquid and the inorganic base liquid in the load liquid is 3-5:5-7.

[0014] Preferably, in step a2, the weight of the foamed iron immersed in each liter of the loading liquid is 140-170 g.

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

[0016] b1. Add biphenyl-3,3',5,5'-tetracarboxylic acid, benzoyl acetone, nickel sulfate, triethylamine and sodium hydroxide to deionized water and mix to form a coordination polymer synthesis solution;

[0017] b2. The intermediate A was immersed in the coordination polymer synthesis solution, heated to 70-90 ° C, reacted for 80-92 hours, cooled to room temperature, and the foamed iron sample was removed, washed with deionized water, and dried at room temperature for 8-12 hours to obtain a surface loaded with [Ni (C 16 H6O8)2(C 10 H 10 O2)] n The foamed iron of the coordination polymer is denoted as intermediate B.

[0018] Preferably, in step b1, per liter of the coordination polymer synthesis liquid, the amount of biphenyl-3,3',5,5'-tetracarboxylic acid added is 130-170 g, the amount of benzoyl acetone added is 30-80 g, the amount of nickel sulfate added is 20-50 g, the amount of triethylamine added is 20-50 mL, and the amount of sodium hydroxide added is 50-100 g.

[0019] Preferably, in step b2, the weight of the intermediate A immersed in each liter of the coordination polymer synthesis solution is 130-180 g.

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

[0021] c1. Add gallium nitrate, ammonium molybdate, ammonium persulfate and sodium metabisulfite to deionized water and mix to form a crystallization solution;

[0022] c2. The intermediate B is immersed in the crystallization solution, heated to 100-120 ° C, reacted for 8-12 hours, cooled to room temperature, and then the foamed iron sample is taken out, washed with deionized water, and dried at room temperature for 10-12 hours to complete the GaMo4S8 nanoparticles in [Ni (C 16 H6O8)2(C 10 H 10 O2)] n The crystals are embedded on the surface of the coordination polymer to finally obtain the visible light catalytic material.

[0023] Preferably, in step c1, the concentration of gallium nitrate in the crystallization solution is 120-150 g / L, the concentration of ammonium molybdate is 160-220 g / L, the concentration of ammonium persulfate is 40-60 g / L, and the concentration of sodium pyrosulfite is 70-90 g / L.

[0024] Preferably, in step c2, the weight of the intermediate B immersed in each liter of the crystallization solution is 160-190 g.

[0025] The positive effect of the present invention is that the visible light catalytic material prepared by the method of the present invention has [Ni(C 16 H6O8)2(C 10 H 10 O2)]n The nickel ion of the coordination polymer is hexacoordinated, and the nickel ion forms coordination bonds with two carbonyl oxygen atoms of a benzoyl acetone and four oxygen atoms of carboxylate ions of two different biphenyl-3,3',5,5'-tetracarboxylic acids, thereby forming [Ni(C 16 H6O8)2(C 10 H 10 O2)] n The structural unit of coordination polymer Ni(C 16 H6O8)2(C 10 H 10 O2), the structural unit forms a coordination bond with the adjacent nickel ion through the oxygen atom of the carboxylate ion of biphenyl-3,3',5,5'-tetracarboxylic acid, forming a repeating structure of [Ni(C 16 H6O8)2(C 10 H 10 O2)] n In addition, GaMo4S8 nanoparticles are dispersed and embedded in [Ni(C 16 H6O8)2(C 10 H 10 O2)] n Coordination polymer, GaMo4S8 nanoparticles are cubic crystals with a space group of F-43m (216). GaMo4S8 nanoparticles have a suitable bandgap and a large active surface area, so they have excellent visible light photocatalytic activity; [Ni(C 16 H6O8)2(C 10 H 10 O2)] n The coordination polymer has a wide visible light absorption range and can effectively inhibit the recombination of photogenerated electrons and photogenerated holes, generate sufficient active free radicals, and effectively reduce the activation energy of the atenolol degradation reaction during the photocatalytic degradation of atenolol.

[0026] In conclusion, the visible light catalytic material prepared according to the present invention has high-efficiency and excellent atenolol photocatalytic degradation performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 It is a schematic diagram of the preparation process of the visible light catalytic material of the present invention;

[0028] Figure 2 is a schematic diagram of the microstructure of the visible light catalytic material of the present invention;

[0029] Figure 3 is the relative concentration of residual atenolol in the simulated atenolol-containing sewage treated with a concentration of 10 mg / L in Example 1, Comparative Example 1 and Comparative Example 2 of the present invention;

[0030] Figure 4 It is the relative concentration of residual atenolol in the simulated atenolol-containing sewage with a treatment concentration of 20 mg / L in Example 1, Comparative Example 1 and Comparative Example 2 of the present invention. DETAILED DESCRIPTION

[0031] Reference Figure 1 The present invention provides a method for preparing a visible light catalytic material for degrading wastewater containing atenolol, comprising the following steps:

[0032] Step [1] Loading [Ni(C 10 H 10 O2)2] coordination compound, specifically including the following operations:

[0033] a1. Add hexaammine nickel chloride, nickel sulfate and trimethylamine oxide to deionized water and mix to form an inorganic base liquid having a hexaammine nickel chloride concentration of 5 to 20 g / L, a nickel sulfate concentration of 120 to 160 g / L and a trimethylamine oxide concentration of 40 to 80 g / L; add benzoyl acetone to ethanol to form an organic additive liquid having a benzoyl acetone concentration of 60 g / L-90 g / L; add the organic additive liquid to the inorganic base liquid in a volume ratio of 3 to 5:5 to 7 to form a loading liquid;

[0034] a2. The foamed iron sample was immersed in the load liquid and used as the cathode (the weight of the foamed iron immersed in each liter of the load liquid was 140-170 g), and the stainless steel plate was used as the anode. The electrophoretic deposition was carried out at a constant voltage of 30 V to 60 V at room temperature for 20 to 30 minutes to obtain a surface loaded with [Ni(C 10 H 10 O2)2] coordination compound, denoted as intermediate A. 10 H 10 O2)2] coordination compound structure formula is:

[0035]

[0036] Step [2]: Loading [Ni(C 10 H 10 O2)2] coordination compound is converted to [Ni(C 16 H6O8)2(C 10 H 10 O2)] n Coordination polymer, specifically including the following operations:

[0037] b1. Add biphenyl-3,3',5,5'-tetracarboxylic acid, benzoyl acetone, nickel sulfate, triethylamine and sodium hydroxide to deionized water and mix to form a coordination polymer synthesis solution; wherein, per liter of the coordination polymer synthesis solution, the amount of biphenyl-3,3',5,5'-tetracarboxylic acid added is 130 to 170 g, the amount of benzoyl acetone added is 30 to 80 g, the amount of nickel sulfate added is 20 to 50 g, the amount of triethylamine added is 20 to 50 mL, and the amount of sodium hydroxide added is 50 to 100 g;

[0038] b2. The intermediate A is immersed in the coordination polymer synthesis solution (the weight of the intermediate A immersed in each liter of the coordination polymer synthesis solution is 130-180g), the temperature is raised to 70-90°C, the reaction is carried out for 80-92 hours, and the foamed iron sample is taken out, washed with deionized water, and dried at room temperature for 8-12 hours to obtain a surface loaded with [Ni(C 16 H6O8)2(C 10 H 10 O2)] n The foamed iron of the coordination polymer is recorded as intermediate B. 16 H6O8)2(C 10 H 10 O2)] n The structure of the coordination polymer is:

[0039]

[0040] Step [3] In [Ni(C 16 H6O8)2(C 10 H 10 O2)] n The surface of the coordination polymer is embedded with GaMo4S8 nanoparticles, which specifically includes the following operations:

[0041] c1. Gallium nitrate, ammonium molybdate, ammonium persulfate and sodium metabisulfite are added to deionized water to form a crystal solution having a gallium nitrate concentration of 120 to 150 g / L, an ammonium molybdate concentration of 160 to 220 g / L, an ammonium persulfate concentration of 40 to 60 g / L, and a sodium metabisulfite concentration of 70 to 90 g / L;

[0042] c2. The intermediate B is immersed in the crystallization solution (the weight of the intermediate B immersed in each liter of the crystallization solution is 160-190 g), heated to 100-120 ° C, reacted for 8-12 hours, cooled to room temperature, and then the foamed iron sample is taken out, washed with deionized water, and dried at room temperature for 10-12 hours to complete the GaMo4S8 nanoparticles in [Ni(C 16 H6O8)2(C 10 H 10 O2)] nThe visible light catalytic material is finally obtained by crystallization inlay on the surface of the coordination polymer, and its microstructure schematic diagram is shown in Figure 2 shown.

[0043] The preferred embodiments of the present invention are described below by way of example.

[0044] Example 1

[0045] Preferred embodiment 1 of the present invention provides a method for preparing a visible light catalytic material for degrading wastewater containing atenolol, comprising the following steps:

[0046] Step [1] Loading [Ni(C 10 H 10 O2)2] coordination compound, specifically including the following operations:

[0047] a1. The nickel chloride hexaamine, nickel sulfate and trimethylamine oxide were added to deionized water and mixed to form an inorganic base liquid having a nickel chloride concentration of 12 g / L, a nickel sulfate concentration of 140 g / L, and a trimethylamine oxide concentration of 70 g / L; benzoyl acetone was added to ethanol to form an organic additive liquid having a benzoyl acetone concentration of 80 g / L; the organic additive liquid was added to the inorganic base liquid in a volume ratio of 5:7 to form a load liquid;

[0048] a2. The foamed iron sample was immersed in the load liquid and used as the cathode (the weight of the foamed iron immersed in each liter of the load liquid was 160 g), the stainless steel plate was used as the anode, and electrophoretic deposition was performed at a constant voltage of 50 V at room temperature for 28 minutes to obtain a surface loaded with [Ni(C 10 H 10 O2)2] coordination compound, recorded as intermediate A.

[0049] Step [2]: Loading [Ni(C 10 H 10 O2)2] coordination compound is converted to [Ni(C 16 H6O8)2(C 10 H 10 O2)] n Coordination polymer, specifically including the following operations:

[0050] b1. Add biphenyl-3,3',5,5'-tetracarboxylic acid, benzoyl acetone, nickel sulfate, triethylamine and sodium hydroxide to deionized water and mix to form a coordination polymer synthesis solution; wherein, per liter of the coordination polymer synthesis solution, biphenyl-3,3',5,5'-tetracarboxylic acid is added in an amount of 160g, benzoyl acetone is added in an amount of 70g, nickel sulfate is added in an amount of 40g, triethylamine is added in an amount of 40mL, and sodium hydroxide is added in an amount of 70g;

[0051] b2. The intermediate A was immersed in the coordination polymer synthesis solution (the weight of the intermediate A immersed in each liter of the coordination polymer synthesis solution was 170 g), the temperature was raised to 80 ° C, the reaction was carried out for 90 hours, and the foamed iron sample was taken out, washed with deionized water, and dried at room temperature for 10 hours to obtain a surface loaded with [Ni(C 16 H6O8)2(C 10 H 10 O2)] n The foamed iron of the coordination polymer is denoted as intermediate B.

[0052] Step [3] In [Ni(C 16 H6O8)2(C 10 H 10 O2)] n The coordination polymer surface is embedded with GaMo4S8 nanoparticles, which specifically includes the following operations:

[0053] c1. Gallium nitrate, ammonium molybdate, ammonium persulfate and sodium metabisulfite were added to deionized water to form a mixture having a gallium nitrate concentration of 140 g / L, an ammonium molybdate concentration of 200 g / L, an ammonium persulfate concentration of 50 g / L, and a sodium metabisulfite concentration of 80 g / L of a crystallization solution;

[0054] c2. The intermediate B was immersed in the crystallization solution (the weight of the intermediate B immersed in each liter of the crystallization solution was 180 g), heated to 110°C, reacted for 10 hours, cooled to room temperature, and then the foamed iron sample was taken out, washed with deionized water, and dried at room temperature for 11 hours to complete the GaMo4S8 nanoparticles in [Ni(C 16 H6O8)2(C 10 H 10 O2)] n The crystals are embedded on the surface of the coordination polymer to finally obtain the visible light catalytic material, which is recorded as Example 1.

[0055] Comparative Example 1

[0056] This comparative example 1 provides a method for preparing a visible light catalytic material for degrading atenolol-containing wastewater, comprising the following steps:

[0057] Step [1] Loading [Ni(C 10 H 10 O2)2] coordination compound, specifically including the following operations:

[0058] a1. The nickel chloride hexaamine, nickel sulfate and trimethylamine oxide were added to deionized water and mixed to form an inorganic base liquid having a nickel chloride concentration of 15 g / L, a nickel sulfate concentration of 125 g / L and a trimethylamine oxide concentration of 60 g / L; benzoyl acetone was added to ethanol to form an organic additive liquid having a benzoyl acetone concentration of 70 g / L; the organic additive liquid was added to the inorganic base liquid in a volume ratio of 4:5 to form a load liquid;

[0059] a2. The foamed iron sample was immersed in the load liquid and used as the cathode (the weight of the foamed iron immersed in each liter of the load liquid was 150 g), the stainless steel plate was used as the anode, and electrophoretic deposition was performed at a constant voltage of 35 V at room temperature for 25 minutes to obtain a surface loaded with [Ni(C 10 H 10 O2)2] coordination compound, recorded as intermediate A.

[0060] Step [2]: Loading [Ni(C 10 H 10 O2)2] coordination compound is converted to [Ni(C 16 H6O8)2(C 10 H 10 O2)] n Coordination polymer, specifically including the following operations:

[0061] b1. Add biphenyl-3,3',5,5'-tetracarboxylic acid, benzoyl acetone, nickel sulfate, triethylamine and sodium hydroxide to deionized water and mix to form a coordination polymer synthesis solution; wherein, per liter of the coordination polymer synthesis solution, biphenyl-3,3',5,5'-tetracarboxylic acid is added in an amount of 140 g, benzoyl acetone is added in an amount of 60 g, nickel sulfate is added in an amount of 30 g, triethylamine is added in an amount of 40 mL, and sodium hydroxide is added in an amount of 70 g;

[0062] b2. The intermediate A was immersed in the coordination polymer synthesis solution (the weight of the intermediate A immersed in each liter of the coordination polymer synthesis solution was 150 g), the temperature was raised to 80 ° C, the reaction was carried out for 84 hours, and the foamed iron sample was taken out, washed with deionized water, and dried at room temperature for 9 hours to obtain a surface loaded with [Ni(C 16 H6O8)2(C 10 H 10 O2)] n The foamed iron of the coordination polymer is recorded as Comparative Example 1.

[0063] Comparative Example 2

[0064] This comparative example 2 provides a method for preparing a visible light catalytic material for degrading atenolol-containing wastewater, comprising the following steps:

[0065] Step [1] Loading [Ni(C 10 H 10 O2)2] coordination compound, specifically including the following operations:

[0066] a1. The nickel chloride hexaamine, nickel sulfate and trimethylamine oxide were added to deionized water and mixed to form an inorganic base liquid having a nickel chloride concentration of 10 g / L, a nickel sulfate concentration of 140 g / L, and a trimethylamine oxide concentration of 60 g / L; benzoyl acetone was added to ethanol to form an organic additive liquid having a benzoyl acetone concentration of 70 g / L; the organic additive liquid was added to the inorganic base liquid in a volume ratio of 3:7 to form a load liquid;

[0067] a2. The foamed iron sample was immersed in the load liquid and used as the cathode (the weight of the foamed iron immersed in each liter of the load liquid was 150 g), the stainless steel plate was used as the anode, and electrophoretic deposition was performed at a constant voltage of 50 V at room temperature for 25 minutes to obtain a surface loaded with [Ni(C 10 H 10 O2)2] coordination compound, recorded as intermediate A.

[0068] Step [2] In [Ni(C 10 H 10 The surface of the coordination compound of O2)2] is inlaid with GaMo4S8 nanoparticles, which specifically includes the following operations:

[0069] c1. Gallium nitrate, ammonium molybdate, ammonium persulfate and sodium metabisulfite were added to deionized water to form a mixture having a gallium nitrate concentration of 140 g / L, an ammonium molybdate concentration of 200 g / L, an ammonium persulfate concentration of 50 g / L, and a sodium metabisulfite concentration of 80 g / L of a crystallization solution;

[0070] c2. The intermediate B was immersed in the crystallization solution (the weight of the intermediate B immersed in each liter of the crystallization solution was 170 g), heated to 110°C, reacted for 9 hours, cooled to room temperature, and then the foamed iron sample was taken out, washed with deionized water, and dried at room temperature for 11 hours to complete the GaMo4S8 nanoparticles in [Ni(C 10 H 10 O2)2] is crystallized on the surface of the coordination compound to finally obtain the visible light catalytic material, which is recorded as Comparative Example 2.

[0071] In order to analyze the performance of the visible light catalytic degradation of atenolol sewage in Example 1, Comparative Example 1 and Comparative Example 2, atenolol was added to deionized water to form atenolol concentration of 10 mg / L and 20 mg / L, respectively. 100 ml of simulated atenolol sewage was poured into a beaker, 10 g of Example 1, Comparative Example 1 and Comparative Example 2 were placed in a beaker, and 150 W and 300 W xenon light sources were used to irradiate Example 1, Comparative Example 1 and Comparative Example 2 for 100 minutes each at a wavelength of 580 nm. The residual atenolol concentration of the simulated atenolol sewage was measured by high performance liquid chromatography. The results are as follows: Figure 3 and Figure 4 Shown by: Figure 3 It can be seen that the residual atenolol relative concentrations of 10g of Example 1 after 100 minutes of visible light catalytic degradation of 10mg / L simulated atenolol-containing sewage under 150W and 300W xenon lamp simulated visible light conditions were only 0.06 and 0.02, respectively. In comparison, the residual atenolol relative concentrations of Comparative Example 1 under the same treatment conditions were as high as 0.56 and 0.39, respectively, and the residual atenolol relative concentrations of Comparative Example 2 were 0.47 and 0.42, respectively. Figure 4 It can be seen that 10g

[0072] In Example 1, after 100 minutes of visible light catalytic degradation of 20 mg / L simulated atenolol-containing wastewater under 150 W and 300 W xenon lamp simulated visible light conditions, the relative concentrations of residual atenolol were only 0.09 and 0.04, respectively, which were much lower than the relative concentrations of residual atenolol in 20 mg / L simulated atenolol-containing wastewater treated in Comparative Example 1 and Comparative Example 2.

[0073] It can be seen that the visible light catalytic material prepared according to the present invention has high-efficiency and excellent atenolol photocatalytic degradation performance.

[0074] To illustrate in further detail, three additional examples are provided below.

[0075] Example 2

[0076] Preferred embodiment 2 of the present invention provides a method for preparing a visible light catalytic material for degrading atenolol-containing wastewater, comprising the following steps:

[0077] Step [1] Loading [Ni(C 10 H 10 O2)2] coordination compound, specifically including the following operations:

[0078] a1. The nickel chloride hexaamine, nickel sulfate and trimethylamine oxide were added to deionized water and mixed to form an inorganic base liquid having a nickel chloride concentration of 5 g / L, a nickel sulfate concentration of 120 g / L, and a trimethylamine oxide concentration of 80 g / L; benzoyl acetone was added to ethanol to form an organic additive liquid having a benzoyl acetone concentration of 60 g / L; the organic additive liquid was added to the inorganic base liquid in a volume ratio of 3:5 to form a load liquid;

[0079] a2. The foamed iron sample was immersed in the load liquid and used as the cathode (the weight of the foamed iron immersed in each liter of the load liquid was 140 g), the stainless steel plate was used as the anode, and electrophoretic deposition was performed at a constant voltage of 30 V at room temperature for 30 minutes to obtain a surface loaded with [Ni(C 10 H 10 O2)2] coordination compound, recorded as intermediate A.

[0080] Step [2]: Loading [Ni(C 10 H 10 O2)2] coordination compound is converted to [Ni(C 16 H6O8)2(C 10 H 10 O2)] n Coordination polymer, specifically including the following operations:

[0081] b1. Add biphenyl-3,3',5,5'-tetracarboxylic acid, benzoyl acetone, nickel sulfate, triethylamine and sodium hydroxide to deionized water and mix to form a coordination polymer synthesis solution; wherein, per liter of the coordination polymer synthesis solution, biphenyl-3,3',5,5'-tetracarboxylic acid is added in an amount of 130 g, benzoyl acetone is added in an amount of 30 g, nickel sulfate is added in an amount of 50 g, triethylamine is added in an amount of 20 mL, and sodium hydroxide is added in an amount of 100 g;

[0082] b2. The intermediate A was immersed in the coordination polymer synthesis solution (the weight of the intermediate A immersed in each liter of the coordination polymer synthesis solution was 130 g), the temperature was raised to 70 ° C, the reaction was carried out for 92 hours, and the foamed iron sample was taken out, washed with deionized water, and dried at room temperature for 8 hours to obtain a surface loaded with [Ni(C 16 H6O8)2(C 10 H 10 O2)] n The foamed iron of the coordination polymer is denoted as intermediate B.

[0083] Step [3] In [Ni(C 16 H6O8)2(C 10 H 10 O2)] nThe surface of the coordination polymer is embedded with GaMo4S8 nanoparticles, which specifically includes the following operations:

[0084] c1. Gallium nitrate, ammonium molybdate, ammonium persulfate and sodium metabisulfite were added to deionized water to form a mixture of gallium nitrate concentration of 120 g / L, ammonium molybdate concentration of 160 g / L, ammonium persulfate concentration of 60 g / L, sodium metabisulfite concentration of 90 g / L of crystallization liquid;

[0085] c2. The intermediate B was immersed in the crystallization solution (the weight of the intermediate B immersed in each liter of the crystallization solution was 160 g), heated to 100 ° C, reacted for 12 hours, cooled to room temperature, and then the foamed iron sample was taken out, washed with deionized water, and dried at room temperature for 10 hours to complete the GaMo4S8 nanoparticles in [Ni(C 16 H6O8)2(C 10 H 10 O2)] n The crystals are embedded on the surface of the coordination polymer to finally obtain the visible light catalytic material.

[0086] Example 3

[0087] Preferred embodiment 3 of the present invention provides a method for preparing a visible light catalytic material for degrading wastewater containing atenolol, comprising the following steps:

[0088] Step [1] Loading [Ni(C 10 H 10 O2)2] coordination compound, specifically including the following operations:

[0089] a1. The nickel chloride hexaamine, nickel sulfate and trimethylamine oxide were added to deionized water and mixed to form an inorganic base liquid having a nickel chloride concentration of 20 g / L, a nickel sulfate concentration of 160 g / L, and a trimethylamine oxide concentration of 40 g / L; benzoyl acetone was added to ethanol to form an organic additive liquid having a benzoyl acetone concentration of 90 g / L; the organic additive liquid was added to the inorganic base liquid in a volume ratio of 5:7 to form a load liquid;

[0090] a2. The foamed iron sample was immersed in the load liquid and used as the cathode (the weight of the foamed iron immersed in each liter of the load liquid was 170 g), the stainless steel plate was used as the anode, and electrophoretic deposition was performed at a constant voltage of 60 V at room temperature for 20 minutes to obtain a surface loaded with [Ni(C 10 H 10 O2)2] coordination compound, recorded as intermediate A.

[0091] Step [2]: Loading [Ni(C 10 H 10O2)2] coordination compound is converted to [Ni(C 16 H6O8)2(C 10 H 10 O2)] n Coordination polymer, specifically including the following operations:

[0092] b1. Add biphenyl-3,3',5,5'-tetracarboxylic acid, benzoyl acetone, nickel sulfate, triethylamine and sodium hydroxide to deionized water and mix to form a coordination polymer synthesis solution; wherein, per liter of the coordination polymer synthesis solution, biphenyl-3,3',5,5'-tetracarboxylic acid is added in an amount of 170 g, benzoyl acetone is added in an amount of 80 g, nickel sulfate is added in an amount of 20 g, triethylamine is added in an amount of 50 mL, and sodium hydroxide is added in an amount of 50 g;

[0093] b2. The intermediate A was immersed in the coordination polymer synthesis solution (the weight of the intermediate A immersed in each liter of the coordination polymer synthesis solution was 180 g), the temperature was raised to 90 ° C, the reaction was carried out for 80 hours, and the foamed iron sample was taken out, washed with deionized water, and dried at room temperature for 12 hours to obtain a surface loaded with [Ni(C 16 H6O8)2(C 10 H 10 O2)] n The foamed iron of the coordination polymer is denoted as intermediate B.

[0094] Step [3] In [Ni(C 16 H6O8)2(C 10 H 10 O2)] n The surface of the coordination polymer is embedded with GaMo4S8 nanoparticles, which specifically includes the following operations:

[0095] c1. Gallium nitrate, ammonium molybdate, ammonium persulfate and sodium metabisulfite were added to deionized water to form a mixture having a gallium nitrate concentration of 150 g / L, an ammonium molybdate concentration of 220 g / L, an ammonium persulfate concentration of 40 g / L, and a sodium metabisulfite concentration of 70 g / L of a crystallization solution;

[0096] c2. The intermediate B was immersed in the crystallization solution (the weight of the intermediate B immersed in each liter of the crystallization solution was 190 g), heated to 120°C, reacted for 8 hours, cooled to room temperature, and then the foamed iron sample was taken out, washed with deionized water, and dried at room temperature for 12 hours to complete the GaMo4S8 nanoparticles in [Ni(C 16 H6O8)2(C 10 H 10 O2)] n The crystals are embedded on the surface of the coordination polymer to finally obtain the visible light catalytic material.

[0097] Example 4

[0098] Preferred embodiment 4 of the present invention provides a method for preparing a visible light catalytic material for degrading wastewater containing atenolol, comprising the following steps:

[0099] Step [1] Loading [Ni(C 10 H 10 O2)2] coordination compound, specifically including the following operations:

[0100] a1. The nickel chloride hexaamine, nickel sulfate and trimethylamine oxide were added to deionized water and mixed to form an inorganic base liquid having a nickel chloride concentration of 12 g / L, a nickel sulfate concentration of 140 g / L, and a trimethylamine oxide concentration of 60 g / L; benzoyl acetone was added to ethanol to form an organic additive liquid having a benzoyl acetone concentration of 75 g / L; the organic additive liquid was added to the inorganic base liquid in a volume ratio of 5:6 to form a load liquid;

[0101] a2. The foamed iron sample was immersed in the load liquid and used as the cathode (the weight of the foamed iron immersed in each liter of the load liquid was 155 g), the stainless steel plate was used as the anode, and electrophoretic deposition was performed at a constant voltage of 45 V at room temperature for 25 minutes to obtain a surface loaded with [Ni(C 10 H 10 O2)2] coordination compound, recorded as intermediate A.

[0102] Step [2]: Loading [Ni(C 10 H 10 O2)2] coordination compound is converted to [Ni(C 16 H6O8)2(C 10 H 10 O2)] n Coordination polymer, specifically including the following operations:

[0103] b1. Add biphenyl-3,3',5,5'-tetracarboxylic acid, benzoyl acetone, nickel sulfate, triethylamine and sodium hydroxide to deionized water and mix to form a coordination polymer synthesis solution; wherein, per liter of the coordination polymer synthesis solution, biphenyl-3,3',5,5'-tetracarboxylic acid is added in an amount of 150g, benzoyl acetone is added in an amount of 55g, nickel sulfate is added in an amount of 35g, triethylamine is added in an amount of 35mL, and sodium hydroxide is added in an amount of 75g;

[0104] b2. The intermediate A was immersed in the coordination polymer synthesis solution (the weight of the intermediate A immersed in each liter of the coordination polymer synthesis solution was 155 g), the temperature was raised to 80 ° C, the reaction was carried out for 86 hours, and the foamed iron sample was taken out, washed with deionized water, and dried at room temperature for 10 hours to obtain a surface loaded with [Ni(C 16H6O8)2(C 10 H 10 O2)] n The foamed iron of the coordination polymer is denoted as intermediate B.

[0105] Step [3] In [Ni(C 16 H6O8)2(C 10 H 10 O2)] n The coordination polymer surface is embedded with GaMo4S8 nanoparticles, which specifically includes the following operations:

[0106] c1. Gallium nitrate, ammonium molybdate, ammonium persulfate and sodium metabisulfite were added to deionized water to form a crystal solution having a gallium nitrate concentration of 135 g / L, an ammonium molybdate concentration of 190 g / L, an ammonium persulfate concentration of 50 g / L, and a sodium metabisulfite concentration of 70 to 90 g / L;

[0107] c2. The intermediate B was immersed in the crystallization solution (the weight of the intermediate B immersed in each liter of the crystallization solution was 175 g), heated to 110°C, reacted for 10 hours, cooled to room temperature, and then the foamed iron sample was taken out, washed with deionized water, and dried at room temperature for 11 hours to complete the GaMo4S8 nanoparticles in [Ni(C 16 H6O8)2(C 10 H 10 O2)] n The crystals are embedded on the surface of the coordination polymer to finally obtain the visible light catalytic material.

[0108] The above are only preferred embodiments of the present invention. It should be understood that the description of the above embodiments is only used to help understand the method and core ideas of the present invention, and is not used to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, etc. made within the ideas and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing a visible light catalytic material for degrading wastewater containing atenolol, characterized in that: The following steps are included: Step [1] Loading [Ni(C 10 H 10 O2)2] coordination compounds; Step [2]: Loading [Ni(C 10 H 10 O2)2] coordination compound is converted to [Ni(C 16 H6O8)2(C 10 H 10 O2)] n Coordination polymers; Step [3] In [Ni(C 16 H6O8)2(C 10 H 10 O2)] n GaMo4S8 nanoparticles are embedded on the surface of the coordination polymer.

2. The method for preparing a visible light catalytic material for degrading atenolol-containing sewage according to claim 1, characterized in that: The step [1] specifically includes the following operations: a1. Nickel chloride hexammine, nickel sulfate and trimethylamine oxide are added to deionized water and mixed to form an inorganic base liquid; benzoyl acetone is added to ethanol and mixed to form an organic additive liquid; a certain amount of the organic additive liquid is added to the inorganic base liquid and mixed to form a loading liquid; a2. The foamed iron sample was immersed in the loading liquid and used as the cathode, the stainless steel plate was used as the anode, and electrophoretic deposition was performed at a constant voltage of 30V to 60V at room temperature for 20 to 30 minutes to obtain a surface loaded with [Ni(C 10 H 10 O2)2] coordination compound, recorded as intermediate A.

3. The method for preparing a visible light catalytic material for degrading atenolol-containing sewage according to claim 2, characterized in that: In step a1, the concentration of hexaamminenickel chloride in the inorganic base liquid is 5-20 g / L, the concentration of nickel sulfate is 120-160 g / L, and the concentration of trimethylamine oxide is 40-80 g / L; the concentration of benzoylacetone in the organic additive liquid is 60 g / L-90 g / L; and the volume ratio between the organic additive liquid and the inorganic base liquid in the load liquid is 3-5:5-7.

4. The method for preparing a visible light catalytic material for degrading atenolol-containing sewage according to claim 2, characterized in that: In step a2, the weight of the foamed iron immersed in each liter of the loading liquid is 140-170 g.

5. The method for preparing a visible light catalytic material for degrading atenolol-containing sewage according to claim 1, characterized in that: The step [2] specifically includes the following operations: b1. Add biphenyl-3,3',5,5'-tetracarboxylic acid, benzoyl acetone, nickel sulfate, triethylamine and sodium hydroxide to deionized water and mix to form a coordination polymer synthesis solution; b2. The intermediate A was immersed in the coordination polymer synthesis solution, heated to 70-90 ° C, reacted for 80-92 hours, cooled to room temperature, and the foamed iron sample was removed, washed with deionized water, and dried at room temperature for 8-12 hours to obtain a surface loaded with [Ni (C 16 H6O8)2(C 10 H 10 O2)] n The foamed iron of the coordination polymer is denoted as intermediate B.

6. The method for preparing a visible light catalytic material for degrading atenolol-containing sewage according to claim 5, characterized in that: In step b1, per liter of the coordination polymer synthesis liquid, the amount of biphenyl-3,3',5,5'-tetracarboxylic acid added is 130-170 g, the amount of benzoyl acetone added is 30-80 g, the amount of nickel sulfate added is 20-50 g, the amount of triethylamine added is 20-50 mL, and the amount of sodium hydroxide added is 50-100 g.

7. The method for preparing a visible light catalytic material for degrading atenolol-containing wastewater according to claim 5, characterized in that: In step b2, the weight of the intermediate A immersed in each liter of the coordination polymer synthesis solution is 130-180 g.

8. The method for preparing a visible light catalytic material for degrading atenolol-containing sewage according to claim 1, characterized in that: The step [3] specifically includes the following operations: c1. Add gallium nitrate, ammonium molybdate, ammonium persulfate and sodium metabisulfite to deionized water and mix to form a crystallization solution; c2. The intermediate B is immersed in the crystallization solution, heated to 100-120 ° C, reacted for 8-12 hours, cooled to room temperature, and then the foamed iron sample is taken out, washed with deionized water, and dried at room temperature for 10-12 hours to complete the GaMo4S8 nanoparticles in [Ni (C 16 H6O8)2(C 10 H 10 O2)] n The crystals are embedded on the surface of the coordination polymer to finally obtain the visible light catalytic material.

9. The method for preparing a visible light catalytic material for degrading atenolol-containing wastewater according to claim 8, characterized in that: In step c1, the concentration of gallium nitrate in the crystallization solution is 120-150 g / L, the concentration of ammonium molybdate is 160-220 g / L, the concentration of ammonium persulfate is 40-60 g / L, and the concentration of sodium pyrosulfite is 70-90 g / L.

10. The method for preparing a visible light catalytic material for degrading atenolol-containing wastewater according to claim 8, characterized in that: In step c2, the weight of the intermediate B immersed in each liter of the crystallization solution is 160-190 g.

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