Preparation method of composite photocatalytic material for degrading ciprofloxacin in sewage

Abstract

The invention provides a preparation method of a composite photocatalytic material for degrading ciprofloxacin in sewage. The preparation method comprises the following steps: (1) loading a (C12H6N2O3-C4H3NS) n polymer on the surface of a foam iron matrix; (2) converting the (C12H6N2O3-C4H3NS) n polymer loaded on the surface of the foam iron matrix into a [Ni (C12H6N2O3) 2 (C4H3NS) 2] n coordination compound; and (3) converting the [Ni (C12H6N2O3) 2 (C4H3NS) 2] n coordination compound into a [Ni < m > (C12H6N2O3) < 2m > Co < m > (C4H3NS) < 2m >] n coordination polymer. The composite photocatalytic material prepared by the method disclosed by the invention has high ciprofloxacin photocatalytic degradation rate and excellent repeated use photocatalytic stability.

Description

Technical Field

[0001] The invention relates to the technical field of ciprofloxacin sewage treatment, in particular to a method for preparing a composite photocatalytic material for degrading ciprofloxacin in sewage. Background Art

[0002] Ciprofloxacin is a synthetic 4-quinolone based compound. 1 Quinolone antibacterial drugs with cyclopropyl groups introduced at the 100-200 position can selectively inhibit topoisomerase II and topoisomerase IV of bacterial cells, destroy bacterial cell DNA replication and transcription, and inhibit bacterial DNA gyrase to twist bacterial double-stranded DNA into a spiral, destroying the division and proliferation function of bacterial cells. Therefore, it has excellent killing effect on Gram-negative bacteria, Gram-positive bacteria, anaerobic bacteria, mycoplasma, chlamydia, etc. After humans and animals ingest ciprofloxacin, more than 70% of ciprofloxacin is excreted from the body through urine and enters the environment to form ciprofloxacin wastewater. Pharmaceutical companies also produce a large amount of ciprofloxacin wastewater during the preparation of ciprofloxacin. Ciprofloxacin wastewater has serious toxic side effects, can cause direct death of aquatic organisms, can be enriched in aquatic organisms such as fish, has obvious biological toxicity to a variety of organisms, leads to the massive reproduction of antibiotic-resistant bacteria, and poses a direct threat to the human living environment.

[0003] Photocatalytic materials can generate photogenerated electrons and photogenerated holes by absorbing light energy, thereby producing strong oxidizing free radicals to oxidatively degrade pollutants adsorbed on the surface of photocatalytic materials. Therefore, photocatalytic degradation of ciprofloxacin wastewater by photocatalytic materials is an effective treatment method for ciprofloxacin wastewater.

[0004] However, the current photocatalytic materials for the photocatalytic degradation of ciprofloxacin wastewater not only have unsatisfactory performance of photogenerated electrons and photogenerated holes, but also have poor selective adsorption of ciprofloxacin, resulting in low degradation efficiency of ciprofloxacin wastewater and poor repeated stability of ciprofloxacin photocatalytic degradation, which is difficult to meet the requirements of large-scale industrial photocatalytic degradation of ciprofloxacin wastewater. This has also become a bottleneck restricting the development of ciprofloxacin wastewater photocatalytic degradation technology. Summary of the invention

[0005] In order to overcome the shortcomings of the prior art, the present invention provides a method for preparing a composite photocatalytic material for degrading ciprofloxacin in sewage. The composite photocatalytic material prepared by the method has a high efficiency of ciprofloxacin photocatalytic degradation rate and excellent repeated use photocatalytic stability.

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

[0007] The present invention provides a method for preparing a composite photocatalytic material for degrading ciprofloxacin in sewage, comprising the following steps:

[0008] Step [1] Loading (C 12 H 6 N 2 O 3 -C 4 H 3 NS) n polymer;

[0009] Step [2]: Load the foamed iron matrix with (C 12 H 6 N 2 O 3 -C 4 H 3 NS) n The polymer was converted into [Ni(C 12 H 6 N 2 O 3 ) 2 (C 4 H 3 NS) 2 ] n coordination compounds;

[0010] Step [3]: the [Ni(C 12 H 6 N 2 O 3 ) 2 (C 4 H 3 NS) 2 ] n The coordination compound is converted to [Ni m (C 12 H 6 N 2 O 3 ) 2m Co m (C 4 H 3 NS) 2m ] n Coordination polymers.

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

[0012] a1. Add 5-bromothiophene-2-carboxylic acid, urea, sodium hydroxide, and 1,2-benzopyrone into deionized water and mix to form a reaction solution A; heat in a water bath to 40-60°C, react for 5-8 hours, cool to room temperature, filter to obtain a solid phase, and dry at room temperature for 3-5 hours to obtain a precursor reaction product;

[0013] a2. The precursor, diammine silver hydroxide, ammonium persulfate, and 2,2'-bipyridine-4,4'-dicarboxylic acid were added to deionized water and mixed to form a reaction solution B; the foamed iron sample was immersed in the reaction solution B, heated to 80-100°C, reacted for 4-7 hours, cooled to room temperature, and the foamed iron sample was taken out and dried at room temperature for 6-8 hours to obtain a surface loaded with (C 12 H 6 N 2 O 3 -C 4 H 3 NS) n Polymer foam iron, recorded as intermediate A.

[0014] Preferably, in step a1, per liter of reaction solution A, the amount of 5-bromothiophene-2-carboxylic acid added is 90-160 g, the amount of urea added is 70-100 g, the amount of sodium hydroxide added is 15-30 g, and the amount of 1,2-benzopyrone added is 10-25 g.

[0015] Preferably, in step a2, the amount of precursor added to each liter of reaction liquid B is 90-160 g, the amount of diammine silver hydroxide added is 50-80 g, the amount of ammonium persulfate added is 20-40 g, and the amount of 2,2'-bipyridine-4,4'-dicarboxylic acid added is 120-170 g; the weight of the foamed iron immersed in each liter of the reaction liquid B is 120-170 g.

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

[0017] b1. Add basic nickel carbonate, oxalic acid and sodium periodate to deionized water and mix to form a reaction solution C;

[0018] b2. Add the reaction solution C to a high-pressure reactor, immerse the intermediate A in the reaction solution C, heat to 90-120°C, react for 24-28 hours, cool naturally to room temperature, take out the foamed iron sample, wash with deionized water, and dry at room temperature for 5-7 hours to obtain a surface loaded with [Ni(C 12 H 6 N 2 O 3 ) 2 (C 4 H 3 NS) 2 ] n The foamed iron of the coordination compound is recorded as intermediate B.

[0019] Preferably, in step b1, the amount of basic nickel carbonate added to each liter of the reaction solution C is 140-190 g, the amount of oxalic acid added is 50-80 g, and the amount of sodium periodate added is 30-50 g.

[0020] Preferably, in step b2, the weight of the intermediate A immersed in each liter of the reaction solution C is 130-190 g.

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

[0022] c1. Cobalt nitrate, acetanilide, 5-bromothiophene-2-carboxylic acid and citric acid were added to deionized water and mixed to form a reaction solution D;

[0023] c2. Add the reaction solution D into the autoclave, immerse the intermediate B into the reaction solution D, heat to 110-130°C, react for 30-36 hours, take out the foamed iron sample, wash with deionized water, dry at room temperature for 8-10 hours, and obtain a surface loaded with [Ni m (C 12 H 6 N 2 O 3 ) 2m Co m (C 4 H 3 NS) 2m ] n The foamed iron of the coordination polymer is the composite photocatalytic material.

[0024] Preferably, in step c1, the amount of cobalt nitrate added to each liter of the reaction solution D is 80-120 g, the amount of acetanilide added is 40-70 g, the amount of 5-bromothiophene-2-carboxylic acid added is 30-50 g, and the amount of citric acid added is 40-80 g.

[0025] Preferably, in step c2, the weight of the intermediate B immersed in each liter of the reaction solution D is 170-230 g.

[0026] The positive effect of the present invention is that the composite photocatalytic material prepared by the method of the present invention has a nickel-cobalt coordination polymer [Ni m (C 12 H 6 N 2 O 3 ) 2m Co m (C 4 H 3 NS) 2m ] n , which is (C 12 H 6 N 2 O 3 -C 4 H 3 NS) n The polymer is a two-dimensional network coordination polymer formed by organic ligands and nickel ions and cobalt ions; wherein (C12 H 6 N 2 O 3 -C 4 H 3 NS) n The polymer is C 12 H 6 N 2 O 3 -C 4 H 3 NS is a one-dimensional chain polymer with one (C 12 H 6 N 2 O 3 -C 4 H 3 NS) n The polymer molecular chain and one side (C 12 H 6 N 2 O 3 -C 4 H 3 NS) n The C of the polymer chain 12 H 6 N 2 O 3 -C 4 H 3 C in NS unit 12 H 6 N 2 O 3 The four nitrogen atoms provide lone pairs of electrons to form four coordination bonds with nickel ions. 12 H 6 N 2 O 3 -C 4 H 3 C in NS unit 4 H 3 The two nitrogen atoms and two sulfur atoms of NS form four coordination bonds with the cobalt ion, thus forming a Ni(C 12 H 6 N 2 O 3 ) 2 Co(C 4 H 3 NS) 2 Based on the above structural characteristics, Ni(C 12 H 6 N 2 O 3 ) 2 Co(C 4 H 3 NS)2 Co(C 4 H 3 NS) 2 Ciprofloxacin N 1 The cyclopropyl group at the 2nd position has a strong adsorption effect, which can achieve strong selective adsorption of ciprofloxacin; in addition, the nickel-cobalt coordination polymer [Ni m (C 12 H 6 N 2 O 3 ) 2m Co m (C 4 H 3 NS) 2m ] n It not only has a delocalized π bond but also has a suitable bandgap width, which makes it have good photogenerated electron and photogenerated hole performance, and helps to inhibit the recombination of photogenerated electrons and photogenerated holes, thereby promoting the generation of peroxyl radicals·O in the process of photocatalytic degradation of ciprofloxacin in wastewater. 2 - , and the generation of OH free radicals to break the quinoline ring structure of ciprofloxacin, thereby achieving effective degradation of ciprofloxacin in wastewater.

[0027] In conclusion, the composite photocatalytic material prepared according to the present invention has a high efficiency of ciprofloxacin photocatalytic degradation rate and excellent photocatalytic stability for repeated use. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0029] Figure 2 It is a schematic diagram of the microstructure of the composite photocatalytic material of the present invention;

[0030] Figure 3 The relative concentration of residual ciprofloxacin in the simulated ciprofloxacin-containing wastewater by photocatalytic degradation under visible light in Example 1, Comparative Example 1 and Comparative Example 2 of the present invention;

[0031] Figure 4 The relative concentration of residual ciprofloxacin in the simulated ciprofloxacin-containing wastewater subjected to photocatalytic degradation under ultraviolet light in Example 1, Comparative Example 1 and Comparative Example 2 of the present invention;

[0032] Figure 5 The relationship between the number of times Example 1, Comparative Example 1, and Comparative Example 2 are used repeatedly under visible light to treat simulated ciprofloxacin-containing wastewater and the relative concentration of residual ciprofloxacin;

[0033] Figure 6The relationship between the number of times Example 1, Comparative Example 1 and Comparative Example 2 are used repeatedly under ultraviolet light to treat simulated ciprofloxacin-containing wastewater and the relative concentration of residual ciprofloxacin. DETAILED DESCRIPTION

[0034] Reference Figure 1 The present invention provides a method for preparing a composite photocatalytic material for degrading ciprofloxacin in sewage, comprising the following steps:

[0035] Step [1] Loading (C 12 H 6 N 2 O 3 -C 4 H 3 NS) n Polymer, specifically including the following operations:

[0036] a1. Add 5-bromothiophene-2-carboxylic acid, urea, sodium hydroxide, and 1,2-benzopyrone to deionized water and mix to form a reaction solution A; heat in a water bath to 40-60°C, react for 5-8 hours, cool to room temperature, filter to obtain a solid phase, and dry at room temperature for 3-5 hours to obtain a precursor reaction product; wherein, per liter of reaction solution A, the amount of 5-bromothiophene-2-carboxylic acid added is 90-160g, the amount of urea added is 70-100g, the amount of sodium hydroxide added is 15-30g, and the amount of 1,2-benzopyrone added is 10-25g. The generation reaction of the precursor reaction product in this step is:

[0037]

[0038] a2. The precursor, diamine silver hydroxide, ammonium persulfate, and 2,2'-bipyridine-4,4'-dicarboxylic acid are added to deionized water and mixed to form a reaction solution B (the amount of the precursor added per liter of reaction solution B is 90 to 160 g, the amount of diamine silver hydroxide added is 50 to 80 g, the amount of ammonium persulfate added is 20 to 40 g, and the amount of 2,2'-bipyridine-4,4'-dicarboxylic acid added is 120 to 170 g); the foamed iron sample is immersed in the reaction solution B (the weight of the foamed iron immersed in the reaction solution B per liter is 120-170 g), heated to 80-100 ° C, reacted for 4-7 hours, cooled to room temperature, the foamed iron sample is taken out, and dried at room temperature for 6-8 hours to obtain a surface load of (C 12 H 6 N 2 O 3 -C 4 H 3 NS) n The foamed iron of the polymer is recorded as intermediate A. 12 H 6 N2 O 3 -C 4 H 3 NS) n The polymer formation reaction is:

[0039]

[0040] Step [2]: Load the foamed iron matrix with (C 12 H 6 N 2 O 3 -C 4 H 3 NS) n The polymer was converted into [Ni(C 12 H 6 N 2 O 3 ) 2 (C 4 H 3 NS) 2 ] n Coordination compounds, specifically including the following operations:

[0041] b1. Add basic nickel carbonate, oxalic acid and sodium periodate to deionized water and mix to form a reaction solution C; wherein, per liter of the reaction solution C, the amount of basic nickel carbonate added is 140 to 190 g, the amount of oxalic acid added is 50 to 80 g, and the amount of sodium periodate added is 30 to 50 g.

[0042] b2. Add the reaction solution C to a high-pressure reactor, immerse the intermediate A in the reaction solution C (the weight of the intermediate A immersed in each liter of the reaction solution C is 130-190 g), heat to 90-120 ° C, react for 24-28 hours, cool naturally to room temperature, take out the foamed iron sample, wash with deionized water and dry at room temperature for 5-7 hours to obtain a surface loaded with [Ni(C 12 H 6 N 2 O 3 ) 2 (C 4 H 3 NS) 2 ] n The foamed iron of the coordination compound is recorded as intermediate B. 12 H 6 N 2 O 3 ) 2 (C 4 H 3 NS) 2 ] n The formation reaction of the coordination compound is:

[0043]

[0044] Step [3]: the [Ni(C 12 H 6 N 2 O 3 ) 2 (C 4 H 3 NS) 2 ] n The coordination compound is converted to [Ni m (C 12 H 6 N 2 O 3 ) 2m Co m (C 4 H 3 NS) 2m ] n Coordination polymer, specifically including the following operations:

[0045] c1. Add cobalt nitrate, acetanilide, 5-bromothiophene-2-carboxylic acid and citric acid to deionized water and mix to form a reaction solution D; wherein, per liter of the reaction solution D, the amount of cobalt nitrate added is 80 to 120 g, the amount of acetanilide added is 40 to 70 g, the amount of 5-bromothiophene-2-carboxylic acid added is 30 to 50 g, and the amount of citric acid added is 40 to 80 g.

[0046] c2. Add the reaction solution D into the autoclave, immerse the intermediate B into the reaction solution D (the weight of the intermediate B immersed in each liter of the reaction solution D is 170-230 g), heat to 110-130 ° C, react for 30-36 hours, take out the foamed iron sample, wash with deionized water, dry at room temperature for 8-10 hours, and obtain a surface loaded with [Ni m (C 12 H 6 N 2 O 3 ) 2m Co m (C 4 H 3 NS) 2m ] n The foamed iron of the coordination polymer is the composite photocatalytic material (its microstructure is shown in FIG. Figure 2 As shown). In this step, [Ni m (C 12 H 6 N 2 O 3 ) 2m Co m (C 4 H3 NS) 2m ] n The formation reaction of coordination polymer is:

[0047]

[0048] Among them, [Ni m (C 12 H 6 N 2 O 3 ) 2m Co m (C 4 H 3 NS) 2m ] n Ni(C 12 H 6 N 2 O 3 ) 2 Co(C 4 H 3 NS) 2 It is a two-dimensional network coordination polymer with a repeating unit, and its structural formula is:

[0049]

[0050] In the structural formula, n is the number of repeating units in the X direction (horizontal direction) of the two-dimensional network coordination polymer, and m is the number of repeating units in the Y direction (vertical direction).

[0051] The preferred embodiments of the present invention are described below by way of example.

[0052] Example 1

[0053] Preferred embodiment 1 of the present invention provides a method for preparing a composite photocatalytic material for degrading ciprofloxacin in sewage, comprising the following steps:

[0054] Step [1] Loading (C 12 H 6 N 2 O 3 -C 4 H 3 NS) n Polymer, specifically including the following operations:

[0055] a1. Add 5-bromothiophene-2-carboxylic acid, urea, sodium hydroxide and 1,2-benzopyrone into deionized water and mix to form a reaction solution A; heat to 55°C in a water bath, react for 7 hours, cool to room temperature, filter to obtain a solid phase, and dry at room temperature for 4 hours to obtain a precursor reaction product; wherein, per liter of reaction solution A, the amount of 5-bromothiophene-2-carboxylic acid added is 150 g, the amount of urea added is 90 g, the amount of sodium hydroxide added is 18 g, and the amount of 1,2-benzopyrone added is 20 g.

[0056] a2. The precursor, diamine silver hydroxide, ammonium persulfate, and 2,2'-bipyridine-4,4'-dicarboxylic acid were added to deionized water and mixed to form a reaction solution B (the amount of the precursor added per liter of reaction solution B was 150 g, the amount of diamine silver hydroxide added was 70 g, the amount of ammonium persulfate added was 30 g, and the amount of 2,2'-bipyridine-4,4'-dicarboxylic acid added was 160 g); the foamed iron sample was immersed in the reaction solution B (the weight of the foamed iron immersed in the reaction solution B per liter was 145 g), heated to 95 ° C, reacted for 6 hours, cooled to room temperature, the foamed iron sample was taken out, and dried at room temperature for 7 hours to obtain a surface load of (C 12 H 6 N 2 O 3 -C 4 H 3 NS) n Polymer foam iron, recorded as intermediate A.

[0057] Step [2]: Load the foamed iron matrix with (C 12 H 6 N 2 O 3 -C 4 H 3 NS) n The polymer was converted into [Ni(C 12 H 6 N 2 O 3 ) 2 (C 4 H 3 NS) 2 ] n Coordination compounds, specifically including the following operations:

[0058] b1. Add basic nickel carbonate, oxalic acid and sodium periodate to deionized water and mix to form a reaction solution C; wherein, per liter of the reaction solution C, the amount of basic nickel carbonate added is 185 g, the amount of oxalic acid added is 70 g, and the amount of sodium periodate added is 45 g.

[0059] b2. The reaction solution C was added to a high-pressure reactor, and the intermediate A was immersed in the reaction solution C (the weight of the intermediate A immersed in each liter of the reaction solution C was 175 g), heated to 115 ° C, reacted for 27 hours, and naturally cooled to room temperature. The foamed iron sample was taken out, washed with deionized water, and dried at room temperature for 6 hours to obtain a surface loaded with [Ni(C 12 H 6 N 2 O 3 ) 2 (C 4 H 3 NS) 2 ] n The foamed iron of the coordination compound is recorded as intermediate B.

[0060] Step [3]: the [Ni(C 12 H 6 N 2 O 3 ) 2 (C 4 H 3 NS) 2 ] n The coordination compound is converted to [Ni m (C 12 H 6 N 2 O 3 ) 2m Co m (C 4 H 3 NS) 2m ] n Coordination polymer, specifically including the following operations:

[0061] c1. Add cobalt nitrate, acetanilide, 5-bromothiophene-2-carboxylic acid and citric acid to deionized water and mix to form a reaction solution D; wherein, per liter of the reaction solution D, the amount of cobalt nitrate added is 90 g, the amount of acetanilide added is 50 g, the amount of 5-bromothiophene-2-carboxylic acid added is 35 g, and the amount of citric acid added is 50 g.

[0062] c2. Add the reaction solution D into the autoclave, immerse the intermediate B into the reaction solution D (the weight of the intermediate B immersed in each liter of the reaction solution D is 210 g), heat to 120 ° C, react for 34 hours, take out the foamed iron sample, wash with deionized water, dry at room temperature for 9 hours, and obtain a surface loaded with [Ni m (C 12 H 6 N 2 O 3 ) 2m Co m (C 4 H 3NS) 2m ] n The foamed iron of the coordination polymer is the composite photocatalytic material, which is recorded as Example 1.

[0063] Comparative Example 1

[0064] This comparative example 1 provides a method for preparing a composite photocatalytic material for degrading ciprofloxacin in sewage, comprising the following steps:

[0065] Step [1] Loading (C 12 H 6 N 2 O 3 -C 4 H 3 NS) n Polymer, specifically including the following operations:

[0066] a1. Add 5-bromothiophene-2-carboxylic acid, urea, sodium hydroxide and 1,2-benzopyrone to deionized water and mix to form a reaction solution A; heat to 45°C in a water bath, react for 6 hours, cool to room temperature, filter to obtain a solid phase, and dry at room temperature for 4 hours to obtain a precursor reaction product; wherein, per liter of reaction solution A, the amount of 5-bromothiophene-2-carboxylic acid added is 100 g, the amount of urea added is 80 g, the amount of sodium hydroxide added is 20 g, and the amount of 1,2-benzopyrone added is 15 g.

[0067] a2. The precursor, diamine silver hydroxide, ammonium persulfate, and 2,2'-bipyridine-4,4'-dicarboxylic acid were added to deionized water and mixed to form a reaction solution B (the amount of the precursor added per liter of reaction solution B was 110 g, the amount of diamine silver hydroxide added was 55 g, the amount of ammonium persulfate added was 25 g, and the amount of 2,2'-bipyridine-4,4'-dicarboxylic acid added was 130 g); the foamed iron sample was immersed in the reaction solution B (the weight of the foamed iron immersed in the reaction solution B per liter was 135 g), heated to 85 ° C, reacted for 5 hours, cooled to room temperature, the foamed iron sample was taken out, and dried at room temperature for 7 hours to obtain a surface load of (C 12 H 6 N 2 O 3 -C 4 H 3 NS) n The polymer foam iron is recorded as Comparative Example 1.

[0068] Comparative Example 2

[0069] This comparative example 2 provides a method for preparing a composite photocatalytic material for degrading ciprofloxacin in sewage, comprising the following steps:

[0070] Step [1] Loading (C 12H 6 N 2 O 3 -C 4 H 3 NS) n Polymer, specifically including the following operations:

[0071] a1. Add 5-bromothiophene-2-carboxylic acid, urea, sodium hydroxide and 1,2-benzopyrone into deionized water and mix to form a reaction solution A; heat to 50°C in a water bath, react for 6 hours, cool to room temperature, filter to obtain a solid phase, and dry at room temperature for 4 hours to obtain a precursor reaction product; wherein, per liter of reaction solution A, the amount of 5-bromothiophene-2-carboxylic acid added is 120 g, the amount of urea added is 90 g, the amount of sodium hydroxide added is 20 g, and the amount of 1,2-benzopyrone added is 20 g.

[0072] a2. The precursor, diamine silver hydroxide, ammonium persulfate, and 2,2'-bipyridine-4,4'-dicarboxylic acid were added to deionized water and mixed to form a reaction solution B (the amount of the precursor added per liter of reaction solution B was 140 g, the amount of diamine silver hydroxide added was 70 g, the amount of ammonium persulfate added was 30 g, and the amount of 2,2'-bipyridine-4,4'-dicarboxylic acid added was 140 g); the foamed iron sample was immersed in the reaction solution B (the weight of the foamed iron immersed in the reaction solution B per liter was 140 g), heated to 90 ° C, reacted for 6 hours, cooled to room temperature, the foamed iron sample was taken out, and dried at room temperature for 7 hours to obtain a surface load of (C 12 H 6 N 2 O 3 -C 4 H 3 NS) n Polymer foam iron, recorded as intermediate A.

[0073] Step [2]: Load the foamed iron matrix with (C 12 H 6 N 2 O 3 -C 4 H 3 NS) n The polymer was converted into [Ni(C 12 H 6 N 2 O 3 ) 2 (C 4 H 3 NS) 2 ] n Coordination compounds, specifically including the following operations:

[0074] b1. Add basic nickel carbonate, oxalic acid and sodium periodate to deionized water and mix to form a reaction solution C; wherein, per liter of the reaction solution C, the amount of basic nickel carbonate added is 180 g, the amount of oxalic acid added is 75 g, and the amount of sodium periodate added is 40 g.

[0075] b2. The reaction solution C was added to a high-pressure reactor, and the intermediate A was immersed in the reaction solution C (the weight of the intermediate A immersed in each liter of the reaction solution C was 150 g), heated to 110 ° C, reacted for 26 hours, and naturally cooled to room temperature. The foamed iron sample was taken out, washed with deionized water, and dried at room temperature for 6 hours to obtain a surface loaded with [Ni(C 12 H 6 N 2 O 3 ) 2 (C 4 H 3 NS) 2 ] n The foamed iron of the coordination compound is recorded as Comparative Example 2.

[0076] In order to analyze the degradation rate of ciprofloxacin wastewater photocatalytically degraded by Example 1, Comparative Example 1 and Comparative Example 2 and its stability in photocatalytic recycling, ciprofloxacin was added to deionized water to form simulated ciprofloxacin wastewater with a ciprofloxacin concentration of 30 mg / L. 1000 ml of simulated ciprofloxacin wastewater was poured into beakers, 10 g of Example 1, Comparative Example 1 and Comparative Example 2 were placed into beakers, and a blank test without photocatalytic material was set up at the same time. The simulated ciprofloxacin wastewater was photodegraded for 60 minutes with a 300W xenon lamp light source under visible light with a wavelength of 500 nm and ultraviolet light with a wavelength of 350 nm. The relative concentration of residual ciprofloxacin in the simulated wastewater after 60 minutes of photocatalytic degradation was as follows: Figure 3 and Figure 4 As shown in the figure, it can be seen that the relative concentrations of residual ciprofloxacin in the simulated sewage photocatalytically degraded under simulated visible light and ultraviolet light conditions in Example 1 are only 0.04 and 0.03 respectively, while the relative concentrations of residual ciprofloxacin in Comparative Example 1 under the same conditions are 0.74 and 0.7 respectively, and the relative concentrations of residual ciprofloxacin in Comparative Example 2 are up to 0.49 and 0.42; under the same conditions, the relative concentrations of residual ciprofloxacin in the group without catalytic material under visible light and ultraviolet light are as high as 0.99 and 0.98. .

[0077] Under the aforementioned simulated visible light and ultraviolet light conditions, Example 1, Comparative Example 1 and Comparative Example 2 were used repeatedly to treat the simulated ciprofloxacin wastewater (each time for photocatalytic degradation for 60 minutes). The relationship between the number of uses and the relative concentration of residual ciprofloxacin was as follows: Figure 5 and Figure 6As shown in the figure, it can be seen that the relative concentrations of residual ciprofloxacin in Example 1 for photocatalytic degradation of simulated ciprofloxacin wastewater with a concentration of 30 mg / L when recycled for the fourth time under visible light and ultraviolet light conditions are only 0.09 and 0.08, respectively, which are much lower than the relative concentrations of residual ciprofloxacin in Comparative Example 1 and Comparative Example 2 when recycled for the fourth time (0.94 and 0.91, 0.73 and 0.62, respectively). Obviously, Example 1 has stable and efficient recyclable characteristics.

[0078] In summary, the composite photocatalytic material prepared according to the present invention has a high efficiency of ciprofloxacin photocatalytic degradation rate and excellent photocatalytic stability for repeated use.

[0079] To illustrate in further detail, three additional examples are provided below.

[0080] Example 2

[0081] Preferred embodiment 2 of the present invention provides a method for preparing a composite photocatalytic material for degrading ciprofloxacin in sewage, comprising the following steps:

[0082] Step [1] Loading (C 12 H 6 N 2 O 3 -C 4 H 3 NS) n Polymer, specifically including the following operations:

[0083] a1. Add 5-bromothiophene-2-carboxylic acid, urea, sodium hydroxide and 1,2-benzopyrone into deionized water and mix to form a reaction solution A; heat to 40°C in a water bath, react for 8 hours, cool to room temperature, filter to obtain a solid phase, and dry at room temperature for 5 hours to obtain a precursor reaction product; wherein, per liter of reaction solution A, the amount of 5-bromothiophene-2-carboxylic acid added is 90 g, the amount of urea added is 100 g, the amount of sodium hydroxide added is 15 g, and the amount of 1,2-benzopyrone added is 25 g.

[0084] a2. The precursor, diamine silver hydroxide, ammonium persulfate, and 2,2'-bipyridine-4,4'-dicarboxylic acid were added to deionized water and mixed to form a reaction solution B (the amount of the precursor added per liter of reaction solution B was 90 g, the amount of diamine silver hydroxide added was 80 g, the amount of ammonium persulfate added was 20 g, and the amount of 2,2'-bipyridine-4,4'-dicarboxylic acid added was 120 g); the foamed iron sample was immersed in the reaction solution B (the weight of the foamed iron immersed in the reaction solution B per liter was 120 g), heated to 80 ° C, reacted for 7 hours, cooled to room temperature, the foamed iron sample was taken out, and dried at room temperature for 8 hours to obtain a surface load of (C 12 H 6 N2 O 3 -C 4 H 3 NS) n Polymer foam iron, recorded as intermediate A.

[0085] Step [2]: Load the foamed iron matrix with (C 12 H 6 N 2 O 3 -C 4 H 3 NS) n The polymer was converted to [Ni(C 12 H 6 N 2 O 3 ) 2 (C 4 H 3 NS) 2 ] n Coordination compounds, specifically including the following operations:

[0086] b1. Add basic nickel carbonate, oxalic acid and sodium periodate to deionized water and mix to form a reaction solution C; wherein, per liter of the reaction solution C, the amount of basic nickel carbonate added is 140 g, the amount of oxalic acid added is 50 g, and the amount of sodium periodate added is 50 g.

[0087] b2. The reaction solution C was added to a high-pressure reactor, and the intermediate A was immersed in the reaction solution C (the weight of the intermediate A immersed in each liter of the reaction solution C was 130 g), heated to 90°C, reacted for 28 hours, and naturally cooled to room temperature. The foamed iron sample was taken out, washed with deionized water, and dried at room temperature for 7 hours to obtain a surface loaded with [Ni(C 12 H 6 N 2 O 3 ) 2 (C 4 H 3 NS) 2 ] n The foamed iron of the coordination compound is recorded as intermediate B.

[0088] Step [3]: the [Ni(C 12 H 6 N 2 O 3 ) 2 (C 4 H 3 NS) 2 ] n The coordination compound is converted to [Ni m (C 12 H 6 N2 O 3 ) 2m Co m (C 4 H 3 NS) 2m ] n Coordination polymer, specifically including the following operations:

[0089] c1. Add cobalt nitrate, acetanilide, 5-bromothiophene-2-carboxylic acid and citric acid to deionized water and mix to form a reaction solution D; wherein, per liter of the reaction solution D, the amount of cobalt nitrate added is 80 g, the amount of acetanilide added is 40 g, the amount of 5-bromothiophene-2-carboxylic acid added is 50 g, and the amount of citric acid added is 40 g.

[0090] c2. Add the reaction solution D into the autoclave, immerse the intermediate B into the reaction solution D (the weight of the intermediate B immersed in each liter of the reaction solution D is 170 g), heat to 110 ° C, react for 36 hours, take out the foamed iron sample, wash with deionized water, dry at room temperature for 10 hours, and obtain a surface loaded with [Ni m (C 12 H 6 N 2 O 3 ) 2m Co m (C 4 H 3 NS) 2m ] n The foamed iron of the coordination polymer is the composite photocatalytic material.

[0091] Example 3

[0092] Preferred embodiment 3 of the present invention provides a method for preparing a composite photocatalytic material for degrading ciprofloxacin in sewage, comprising the following steps:

[0093] Step [1] Loading (C 12 H 6 N 2 O 3 -C 4 H 3 NS) n Polymer, specifically including the following operations:

[0094] a1. Add 5-bromothiophene-2-carboxylic acid, urea, sodium hydroxide and 1,2-benzopyrone into deionized water and mix to form a reaction solution A; heat to 60°C in a water bath, react for 5 hours, cool to room temperature, filter to obtain a solid phase, and dry at room temperature for 3 hours to obtain a precursor reaction product; wherein, per liter of reaction solution A, the amount of 5-bromothiophene-2-carboxylic acid added is 160 g, the amount of urea added is 70 g, the amount of sodium hydroxide added is 30 g, and the amount of 1,2-benzopyrone added is 10 g.

[0095] a2. The precursor, diamine silver hydroxide, ammonium persulfate, and 2,2'-bipyridine-4,4'-dicarboxylic acid were added to deionized water and mixed to form a reaction solution B (the amount of the precursor added per liter of reaction solution B was 160 g, the amount of diamine silver hydroxide added was 50 g, the amount of ammonium persulfate added was 40 g, and the amount of 2,2'-bipyridine-4,4'-dicarboxylic acid added was 170 g); the foamed iron sample was immersed in the reaction solution B (the weight of the foamed iron immersed in the reaction solution B per liter was 170 g), heated to 100 ° C, reacted for 4 hours, cooled to room temperature, the foamed iron sample was taken out, and dried at room temperature for 6 hours to obtain a surface load of (C 12 H 6 N 2 O 3 -C 4 H 3 NS) n Polymer foam iron, recorded as intermediate A.

[0096] Step [2]: Load the foamed iron matrix with (C 12 H 6 N 2 O 3 -C 4 H 3 NS) n The polymer was converted into [Ni(C 12 H 6 N 2 O 3 ) 2 (C 4 H 3 NS) 2 ] n Coordination compounds, specifically including the following operations:

[0097] b1. Add basic nickel carbonate, oxalic acid and sodium periodate to deionized water and mix to form a reaction solution C; wherein, per liter of the reaction solution C, the amount of basic nickel carbonate added is 190 g, the amount of oxalic acid added is 80 g, and the amount of sodium periodate added is 30 g.

[0098] b2. Add the reaction solution C into a high-pressure reactor, immerse the intermediate A in the reaction solution C (the weight of the intermediate A immersed in each liter of the reaction solution C is 190 g), heat to 120°C, react for 24 hours, cool naturally to room temperature, take out the foamed iron sample, wash with deionized water and dry at room temperature for 5 hours to obtain a surface loaded with [Ni(C 12 H 6 N 2 O 3 ) 2 (C 4 H 3 NS) 2 ] n The foamed iron of the coordination compound is recorded as intermediate B.

[0099] Step [3]: the [Ni(C 12 H 6 N 2 O 3 ) 2 (C 4 H 3 NS) 2 ] n The coordination compound is converted to [Ni m (C 12 H 6 N 2 O 3 ) 2m Co m (C 4 H 3 NS) 2m ] n Coordination polymer, specifically including the following operations:

[0100] c1. Add cobalt nitrate, acetanilide, 5-bromothiophene-2-carboxylic acid and citric acid to deionized water and mix to form a reaction solution D; wherein, per liter of the reaction solution D, the amount of cobalt nitrate added is 120 g, the amount of acetanilide added is 70 g, the amount of 5-bromothiophene-2-carboxylic acid added is 30 g, and the amount of citric acid added is 80 g.

[0101] c2. Add the reaction solution D into the autoclave, immerse the intermediate B into the reaction solution D (the weight of the intermediate B immersed in each liter of the reaction solution D is 230 g), heat to 130 ° C, react for 30 hours, take out the foamed iron sample, wash with deionized water, dry at room temperature for 8 hours, and obtain a surface loaded with [Ni m (C 12 H 6 N 2 O 3 ) 2m Co m (C 4 H 3NS) 2m ] n The foamed iron of the coordination polymer is the composite photocatalytic material.

[0102] Example 4

[0103] Preferred embodiment 4 of the present invention provides a method for preparing a composite photocatalytic material for degrading ciprofloxacin in sewage, comprising the following steps:

[0104] Step [1] Loading (C 12 H 6 N 2 O 3 -C 4 H 3 NS) n Polymer, specifically including the following operations:

[0105] a1. Add 5-bromothiophene-2-carboxylic acid, urea, sodium hydroxide and 1,2-benzopyrone into deionized water and mix to form a reaction solution A; heat to 50°C in a water bath, react for 6 hours, cool to room temperature, filter to obtain a solid phase, and dry at room temperature for 4 hours to obtain a precursor reaction product; wherein, per liter of reaction solution A, the amount of 5-bromothiophene-2-carboxylic acid added is 125 g, the amount of urea added is 85 g, the amount of sodium hydroxide added is 24 g, and the amount of 1,2-benzopyrone added is 19 g.

[0106] a2. The precursor, diamine silver hydroxide, ammonium persulfate, and 2,2'-bipyridine-4,4'-dicarboxylic acid were added to deionized water and mixed to form a reaction solution B (the amount of the precursor added per liter of reaction solution B was 125 g, the amount of diamine silver hydroxide added was 65 g, the amount of ammonium persulfate added was 30 g, and the amount of 2,2'-bipyridine-4,4'-dicarboxylic acid added was 145 g); the foamed iron sample was immersed in the reaction solution B (the weight of the foamed iron immersed in the reaction solution B per liter was 146 g), heated to 90 ° C, reacted for 5 hours, cooled to room temperature, the foamed iron sample was taken out, and dried at room temperature for 7 hours to obtain a surface load of (C 12 H 6 N 2 O 3 -C 4 H 3 NS) n Polymer foam iron, recorded as intermediate A.

[0107] Step [2]: Load the foamed iron matrix with (C 12 H 6 N 2 O 3 -C 4 H 3 NS) nThe polymer was converted into [Ni(C 12 H 6 N 2 O 3 ) 2 (C 4 H 3 NS) 2 ] n Coordination compounds, specifically including the following operations:

[0108] b1. Add basic nickel carbonate, oxalic acid and sodium periodate to deionized water and mix to form a reaction solution C; wherein, per liter of the reaction solution C, the amount of basic nickel carbonate added is 160 g, the amount of oxalic acid added is 65 g, and the amount of sodium periodate added is 40 g.

[0109] b2. The reaction solution C was added to a high-pressure reactor, and the intermediate A was immersed in the reaction solution C (the weight of the intermediate A immersed in each liter of the reaction solution C was 160 g), heated to 105°C, reacted for 26 hours, and naturally cooled to room temperature. The foamed iron sample was taken out, washed with deionized water, and dried at room temperature for 6 hours to obtain a surface loaded with [Ni(C 12 H 6 N 2 O 3 ) 2 (C 4 H 3 NS) 2 ] n The foamed iron of the coordination compound is recorded as intermediate B.

[0110] Step [3]: the [Ni(C 12 H 6 N 2 O 3 ) 2 (C 4 H 3 NS) 2 ] n The coordination compound is converted to [Ni m (C 12 H 6 N 2 O 3 ) 2m Co m (C 4 H 3 NS) 2m ] n Coordination polymer, specifically including the following operations:

[0111] c1. Add cobalt nitrate, acetanilide, 5-bromothiophene-2-carboxylic acid and citric acid to deionized water and mix to form a reaction solution D; wherein, per liter of the reaction solution D, the amount of cobalt nitrate added is 100 g, the amount of acetanilide added is 55 g, the amount of 5-bromothiophene-2-carboxylic acid added is 40 g, and the amount of citric acid added is 60 g.

[0112] c2. Add the reaction solution D into the autoclave, immerse the intermediate B into the reaction solution D (the weight of the intermediate B immersed in each liter of the reaction solution D is 200 g), heat to 120 ° C, react for 32 hours, take out the foamed iron sample, wash with deionized water, dry at room temperature for 9 hours, and obtain a surface loaded with [Ni m (C 12 H 6 N 2 O 3 ) 2m Co m (C 4 H 3 NS) 2m ] n The foamed iron of the coordination polymer is the composite photocatalytic material.

[0113] The above are only preferred embodiments of the present invention. It should be understood that the description of the above embodiments is only used to help understand the method and core ideas of the present invention, and is not used to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, etc. made within the ideas and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing a composite photocatalytic material for degrading ciprofloxacin in sewage, characterized in that: The following steps are included: Step [1] Loading (C 12 H6N2O3-C4H3NS) n polymer; Step [2]: Load the foamed iron matrix with (C 12 H6N2O3-C4H3NS) n The polymer was converted to [Ni(C 12 H6N2O3)2(C4H3NS)2] n coordination compounds; Step [3]: the [Ni(C 12 H6N2O3)2(C4H3NS)2] n The coordination compound is converted to [Ni m (C 12 H6N2O3) 2m Co m (C4H3NS) 2m ] n Coordination polymers.

2. The method for preparing a composite photocatalytic material for degrading ciprofloxacin in sewage according to claim 1, characterized in that: The step [1] specifically includes the following operations: a1. Add 5-bromothiophene-2-carboxylic acid, urea, sodium hydroxide, and 1,2-benzopyrone into deionized water and mix to form a reaction solution A; heat in a water bath to 40-60°C, react for 5-8 hours, cool to room temperature, filter to obtain a solid phase, and dry at room temperature for 3-5 hours to obtain a precursor reaction product; a2. The precursor, diammine silver hydroxide, ammonium persulfate, and 2,2'-bipyridine-4,4'-dicarboxylic acid were added to deionized water and mixed to form a reaction solution B; the foamed iron sample was immersed in the reaction solution B, heated to 80-100°C, reacted for 4-7 hours, cooled to room temperature, and the foamed iron sample was taken out and dried at room temperature for 6-8 hours to obtain a surface loaded with (C 12 H6N2O3-C4H3NS) n Polymer foam iron, recorded as intermediate A.

3. The method for preparing a composite photocatalytic material for degrading ciprofloxacin in sewage according to claim 2, characterized in that: In step a1, per liter of reaction solution A, the amount of 5-bromothiophene-2-carboxylic acid added is 90-160 g, the amount of urea added is 70-100 g, the amount of sodium hydroxide added is 15-30 g, and the amount of 1,2-benzopyrone added is 10-25 g.

4. The method for preparing a composite photocatalytic material for degrading ciprofloxacin in sewage according to claim 2, characterized in that: In step a2, the amount of precursor added to each liter of reaction solution B is 90-160 g, the amount of diammine silver hydroxide added is 50-80 g, the amount of ammonium persulfate added is 20-40 g, and the amount of 2,2'-bipyridine-4,4'-dicarboxylic acid added is 120-170 g; the weight of the foamed iron immersed in each liter of the reaction solution B is 120-170 g.

5. The method for preparing a composite photocatalytic material for degrading ciprofloxacin in sewage according to claim 1, characterized in that: The step [2] specifically includes the following operations: b1. Add basic nickel carbonate, oxalic acid and sodium periodate to deionized water and mix to form a reaction solution C; b2. Add the reaction solution C to a high-pressure reactor, immerse the intermediate A in the reaction solution C, heat to 90-120°C, react for 24-28 hours, cool naturally to room temperature, take out the foamed iron sample, wash with deionized water, and dry at room temperature for 5-7 hours to obtain a surface loaded with [Ni(C 12 H6N2O3)2(C4H3NS)2] n The foamed iron of the coordination compound is recorded as intermediate B.

6. The method for preparing a composite photocatalytic material for degrading ciprofloxacin in sewage according to claim 5, characterized in that: In step b1, per liter of the reaction solution C, the amount of basic nickel carbonate added is 140-190 g, the amount of oxalic acid added is 50-80 g, and the amount of sodium periodate added is 30-50 g.

7. The method for preparing a composite photocatalytic material for degrading ciprofloxacin in sewage according to claim 5, characterized in that: In step b2, the weight of the intermediate A immersed in each liter of the reaction solution C is 130-190 g.

8. The method for preparing a composite photocatalytic material for degrading ciprofloxacin in sewage according to claim 1, characterized in that: The step [3] specifically includes the following operations: c1. Cobalt nitrate, acetanilide, 5-bromothiophene-2-carboxylic acid and citric acid were added to deionized water and mixed to form a reaction solution D; c2. Add the reaction solution D into the autoclave, immerse the intermediate B into the reaction solution D, heat to 110-130°C, react for 30-36 hours, take out the foamed iron sample, wash with deionized water, dry at room temperature for 8-10 hours, and obtain a surface loaded with [Ni m (C 12 H6N2O3) 2m Co m (C4H3NS) 2m ] n The foamed iron of the coordination polymer is the composite photocatalytic material.

9. The method for preparing a composite photocatalytic material for degrading ciprofloxacin in sewage according to claim 8, characterized in that: In step c1, per liter of the reaction solution D, the amount of cobalt nitrate added is 80-120 g, the amount of acetanilide added is 40-70 g, the amount of 5-bromothiophene-2-carboxylic acid added is 30-50 g, and the amount of citric acid added is 40-80 g.

10. The method for preparing a composite photocatalytic material for degrading ciprofloxacin in sewage according to claim 8, characterized in that: In step c2, the weight of the intermediate B immersed in each liter of the reaction solution D is 170-230 g.

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