Sulfur-modified Fe-polymer-based self-assembled nanosphere and application thereof

Abstract

The invention discloses a sulfur-modified Fe-polymer-based self-assembled nanosphere which is prepared from anhydride, phenylenediamine, ferric salt and thioacetamide according to the mass ratio of 1: (2-8): 1: (4-9), black brown powder is obtained through polymerization and product drying, then a sulfuric acid aqueous solution with the mass concentration of 10%-60% is used for etching, and the sulfur-modified Fe-polymer-based self-assembled nanosphere is obtained. And after etching, putting into a crucible, and calcining at 400-600 DEG C for 2-4 hours to obtain a target product. The N-H bond and the iron element are introduced into the nanosphere, active sites of the nanosphere are increased, the number and the size of holes in the nanosphere are increased through sulfuric acid etching, and therefore the contact area of the nanosphere and reactants is increased, and the catalytic efficiency and the stability are improved. The preparation method is simple to operate, low in cost and less in waste material generation.

Description

Technical Field

[0001] The invention belongs to the field of photocatalytic applications, and specifically relates to a sulfur-modified Fe-polymer-based self-assembled nanosphere and an application of the nanosphere as a catalyst in degrading organic pollutants in wastewater. Background Art

[0002] With the rapid development of science and industry, wastewater discharge is one of the more difficult problems in water pollution. A large amount of wastewater is discharged into rivers, lakes and seas, including medical wastewater, pesticide wastewater, biological wastewater, printing and dyeing wastewater and drug wastewater. These wastewaters usually contain a large amount of organic matter and metal ions, which are not only difficult to degrade, but also produce toxic substances after cracking, which seriously affects the water environment. The organic pollutants in water bodies have complex and diverse structures, are difficult to degrade, and have biological hazards such as toxicity, teratogenicity and mutagenicity. Efficient and convenient water treatment technology is urgently needed for pollution control.

[0003] Photocatalytic technology provides an efficient and environmentally friendly solution for removing these organic pollutants. In order to find non-precious metal catalysts with low price, good catalytic effect and low environmental pollution, many researchers have turned their attention to the research of porous carbon catalysts. Porous carbon nanoflowers are spherical nanocarbon materials with rich interpenetrating or closed pore structures. They are mainly used in photocatalytic and electrocatalytic water treatment materials. This technology is a new type of wastewater treatment technology that does not produce secondary pollution. Porous carbon materials continue to expand their application areas by adjusting pore size, surface area and doping with other elements. They are now widely used in research and production fields such as adsorption, catalysis and energy storage. Porous carbon nanospheres have a wear-resistant spherical morphology, rich and adjustable internal pore structure and easily modifiable surface groups, which can play an important role in the process of multiphase catalytic reactions. Doping metal elements into nanoflower balls can easily cause the loss and shedding of active sites. Therefore, the present invention aims to find a suitable product that can make the metal active sites grow evenly inside the nanospheres, greatly improve the catalytic stability of the nanospheres, and synthesize a catalyst assembled into balls of metal-organic nanosheets with simple process, less waste generation and relatively environmentally friendly in the technical field of adsorption and catalysis, which can effectively catalyze the degradation of organic pollutants in wastewater. Summary of the invention

[0004] In order to overcome the deficiencies of the prior art, the present invention provides a sulfur-modified Fe-polymer-based self-assembled nanosphere.

[0005] A sulfur-modified Fe-polymer-based self-assembled nanosphere is prepared from anhydride, phenylenediamine, iron salt, and thioacetamide in a molar ratio of 1:2-8:1:4-9. The preparation method is as follows:

[0006] (1) dissolving the acid anhydride and the phenylenediamine in an organic solvent A to obtain a solution A, dissolving the iron salt and the thioacetamide in an organic solvent B to obtain a solution B, adding the solution B dropwise to the solution B and then mixing by ultrasonication to obtain a mixed solution; the mass ratio of the acid anhydride to the organic solvent A is 1:18-51, and the mass ratio of the iron salt to the organic solvent B is 1:18-51;

[0007] (2) reacting the mixed solution at a temperature of 160-200° C. for 6-10 hours to obtain a reaction solution;

[0008] (3) centrifuging the reaction solution in step (2), removing the liquid, washing with DMF and methanol respectively, filtering the precipitate, and drying to obtain a dark brown powder;

[0009] (4) etching the dark brown powder prepared in step (3) with a sulfuric acid aqueous solution having a mass concentration of 10% to 60% to obtain an etched dark brown powder;

[0010] (5) The dark brown powder etched with sulfuric acid in step (4) is placed in a crucible and calcined at 400-600° C. for 2-4 hours to obtain the sulfur-modified Fe-polymer-based self-assembled nanospheres, wherein the heating rate of the calcination is 2-5° C. / min. It is specifically recommended that the calcination in step (5) be calcined at 500° C. for 3 hours and heated to 500° C. at a rate of 5° C. / min.

[0011] Furthermore, the acid anhydride is one or more of pyromellitic dianhydride and 3,3',4,4'-benzophenonecarboxylic dianhydride, preferably 3,3',4,4'-benzophenonecarboxylic dianhydride.

[0012] Furthermore, the phenylenediamine is one or more of p-phenylenediamine, o-phenylenediamine or m-phenylenediamine;

[0013] Furthermore, the iron salt is one or more of an organic iron salt and an inorganic iron salt, the organic iron salt is ferric acetylacetonate, and the inorganic iron salt is one or more of ferric chloride and ferric nitrate.

[0014] Preferably, the molar ratio of the acid anhydride, phenylenediamine, iron salt and thioacetamide is 1:2:1:4.

[0015] Furthermore, the reaction in step (2) is carried out at 180° C. for 6 hours to obtain a reaction solution.

[0016] Furthermore, the drying in step (3) is performed at 60° C. in vacuum for 12 hours.

[0017] Furthermore, the mass concentration of the aqueous sulfuric acid solution in step (4) is 50%.

[0018] The present invention also relates to the application of the sulfur-modified Fe-polymer-based self-assembled nanospheres as catalysts in degrading organic pollutants in wastewater.

[0019] The application method is as follows: add sulfur-modified Fe-polymer-based self-assembled nanospheres with a mass concentration of 0.05-1.0% as a catalyst to wastewater containing organic pollutants, oscillate the reaction for 30-60 minutes under light-proof conditions, and then add hydrogen peroxide under light conditions to continue the reaction until it is complete, preferably continuing the reaction for 150 minutes, so that the organic pollutants can be effectively degraded.

[0020] The invention introduces NH bonds and iron elements into nanospheres by copolymerizing acid anhydride, phenylenediamine, iron salt and thioacetamide and then sequentially etching with sulfuric acid and calcining, thereby increasing the active sites of the nanospheres and improving the catalytic activity and catalytic stability of the nanospheres. The sulfuric acid etching increases the number and volume of pores on the nanospheres, thereby increasing the contact area between the nanospheres and reactants and thus improving the catalytic efficiency. The preparation method of the nanospheres is simple to operate, low in cost and generates less waste. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is a scanning electron microscope image of the sulfur-modified Fe-polymer-based self-assembled nanospheres obtained in Example 3 of this case.

[0022] Figure 2 This is the adsorption curve of methamphetamine by the sulfur-modified Fe-polymer-based self-assembled nanospheres obtained in Example 5 of this case.

[0023] Figure 3 This is the adsorption curve of ketamine by the sulfur-modified Fe-polymer-based self-assembled nanospheres obtained in Example 6 of this case. DETAILED DESCRIPTION

[0025] The present invention is further described below by means of specific embodiments, but the protection scope of the present invention is not limited thereto.

[0026] Example 1

[0027] 1.212g3,3',4,4'-dibenzophenonecarboxylic acid dianhydride (1mol) and 0.822g p-phenylenediamine (2mol) were dissolved in 30mL DMF, recorded as solution A. 0.616g anhydrous ferric chloride (1mol) and 1.142g thioacetamide (4mol) were dissolved in 30mL DMF, recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 180℃ for 6h. After the reaction, the reaction liquid was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times respectively. Dry in a vacuum at 60℃. A dark brown powder was obtained.

[0028] The dark brown powder obtained above was etched using 50% sulfuric acid.

[0029] The dark brown powder etched with sulfuric acid was filtered, put into a crucible, and calcined at 500°C for 3 h with a heating rate of 5°C / min to finally obtain sulfur-modified Fe-polymer-based self-assembled nanospheres, denoted as PI-S1-Fe1@C.

[0030] Example 2

[0031] 1.212g3,3',4,4'-dibenzophenonecarboxylic acid dianhydride (1mol) and 0.822g p-phenylenediamine (2mol) were dissolved in 30mL DMF, recorded as solution A. 1.535g ferric nitrate (1mol) and 1.142g thioacetamide (4mol) were dissolved in 30mL DMF, recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 180℃ for 6h. After the reaction, the reaction liquid was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times respectively. Dry in a vacuum at 60℃. A dark brown powder can be obtained.

[0032] The dark brown powder obtained above was etched using 50% sulfuric acid.

[0033] The dark brown powder obtained above was placed in a crucible and calcined at 500°C for 3 h with a heating rate of 5°C / min to finally obtain sulfur-modified Fe-polymer-based self-assembled nanospheres, PI-S1-Fe2@C.

[0034] Example 3

[0035] 1.212g3,3',4,4'-benzophenonecarboxylic acid dianhydride (1mol) and 0.822g p-phenylenediamine (2mol) were dissolved in 30mL DMF, recorded as solution A. 0.308g anhydrous ferric chloride (0.5mol) and 0.767g ferric nitrate (0.5mol) and 1.142g thioacetamide (4mol) were dissolved in 30mL DMF, recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 180℃ for 6h. After the reaction, the reaction liquid was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times respectively. Dry in a vacuum at 60℃. A dark brown powder can be obtained.

[0036] The dark brown powder obtained above was etched using 50% sulfuric acid.

[0037] The dark brown powder obtained above was placed in a crucible and calcined at 500°C for 3 h with a heating rate of 5°C / min, and finally sulfur-modified Fe-polymer-based self-assembled nanospheres were obtained, which were recorded as PI-S1-Fe1 / Fe2@C.

[0038] SEM images are attached. Figure 1

[0039] Example 4

[0040] 1.212g3,3',4,4'-dibenzophenonecarboxylic acid dianhydride (1mol) and 0.822g p-phenylenediamine (2mol) were dissolved in 30mL DMF, recorded as solution A. 1.342g ferric acetylacetonate (1mol) and 1.142g thioacetamide (4mol) were dissolved in 30mL DMF, recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 180℃ for 6h. After the reaction, the reaction liquid was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times respectively. Dry in a vacuum at 60℃. A dark brown powder can be obtained.

[0041] The dark brown powder obtained above was etched using 50% sulfuric acid.

[0042] The dark brown powder obtained above was placed in a crucible and calcined at 500°C for 3 h with a heating rate of 5°C / min, and finally sulfur-modified Fe-polymer-based self-assembled nanospheres were obtained, which were recorded as PI-S1-FA@C.

[0043] Example 5: (Adsorption 1)

[0044] 1.212g3,3',4,4'-benzophenonecarboxylic acid dianhydride (1mol) and 0.822g p-phenylenediamine (2mol) were dissolved in 30mL DMF, recorded as solution A. 0.308g anhydrous ferric chloride (0.5mol) and 0.767g ferric nitrate (0.5mol) and 1.142g thioacetamide (4mol) were dissolved in 30mL DMF, recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 180℃ for 6h. After the reaction, the reaction liquid was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times respectively. Dry in a vacuum at 60℃. A dark brown powder can be obtained.

[0045] The dark brown powder obtained above was etched with 50% sulfuric acid.

[0046] The dark brown powder obtained above was placed in a crucible and calcined at 500 °C for 3 h with a heating rate of 5 °C / min to finally obtain sulfur-modified Fe-polymer-based self-assembled nanospheres, denoted as PI-S1-Fe1 / Fe2@C

[0047] (Adsorption 1).

[0048] The final application is the adsorption of 10 ng / L of methamphetamine within 30 min. The adsorption curve of methamphetamine is shown in the attached figure. Figure 2 .

[0049] Example 6: (Adsorption 2)

[0050] 1.212g3,3',4,4'-benzophenonecarboxylic acid dianhydride (1mol) and 0.822g p-phenylenediamine (2mol) were dissolved in 30mL DMF, recorded as solution A. 0.308g anhydrous ferric chloride (0.5mol) and 0.767g ferric nitrate (0.5mol) and 1.142g thioacetamide (4mol) were dissolved in 30mL DMF, recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 180℃ for 6h. After the reaction, the reaction liquid was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times respectively. Dry in a vacuum at 60℃. A dark brown powder can be obtained.

[0051] The dark brown powder obtained above was etched using 50% sulfuric acid.

[0052] The dark brown powder obtained above was placed in a crucible and calcined at 500 °C for 3 h with a heating rate of 5 °C / min to finally obtain sulfur-modified Fe-polymer-based self-assembled nanospheres, denoted as PI-S1-Fe1 / Fe2@C

[0053] (Adsorption 2).

[0054] The final application is the adsorption of 100 ng / L ketamine within 30 min. The adsorption curve of ketamine by sulfur-modified Fe-polymer-based self-assembled nanospheres is shown in the attached figure. Figure 3 .

[0055] Example 7

[0056] 1.212g3,3',4,4'-dibenzophenonecarboxylic acid dianhydride (1mol) and 0.822g p-phenylenediamine (2mol) were dissolved in 30mL DMF, which was recorded as solution A. 0.616g anhydrous ferric chloride (1mol) and 1.142g thioacetamide (4mol) were dissolved in 30mL DMF, which was recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 160℃ for 6h. After the reaction, the reaction liquid was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times respectively. Dry in a vacuum at 60℃. A dark brown powder can be obtained.

[0057] The dark brown powder obtained above was etched using 50% sulfuric acid.

[0058] The dark brown powder obtained above was placed in a crucible and calcined at 500°C for 3 h with a heating rate of 5°C / min to finally obtain sulfur-modified Fe-polymer-based self-assembled nanospheres, recorded as (PI-S1-Fe1)1@C.

[0059] Example 8

[0060] 1.212g 3,3',4,4'-dibenzophenone carboxylic acid dianhydride (1mol) and 0.822g p-phenylenediamine (2mol) were dissolved in 30mL DMF, recorded as solution A. 0.616g anhydrous ferric chloride (1mol) and 1.142g thioacetamide (4mol) were dissolved in 30mL DMF, recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 200℃ for 6h. After the reaction, wash it with DMF and methanol three times respectively. Dry it in a vacuum at 60℃. A dark brown powder can be obtained.

[0061] The dark brown powder obtained above was etched using 50% sulfuric acid.

[0062] The dark brown powder obtained above was placed in a crucible and calcined at 500°C for 3 h with a heating rate of 5°C / min to finally obtain sulfur-modified Fe-polymer-based self-assembled nanospheres, which were recorded as (PI-S1-Fe1)2@C.

[0063] Example 9

[0064] 1.212g3,3',4,4'-dibenzophenonecarboxylic acid dianhydride (1mol) and 0.822g p-phenylenediamine (2mol) were dissolved in 30mL DMF, recorded as solution A. 0.616g anhydrous ferric chloride (1mol) and 1.142g thioacetamide (4mol) were dissolved in 30mL DMF, recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 170℃ for 6h. After the reaction, the reaction liquid was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times respectively. Dry in a vacuum at 60℃. A dark brown powder can be obtained.

[0065] The dark brown powder obtained above was etched using 50% sulfuric acid.

[0066] The dark brown powder obtained above was placed in a crucible and calcined at 500℃ for 3h with a heating rate of 5℃ / min to finally obtain sulfur-modified Fe-polymer-based self-assembled nanospheres, denoted as (PI-S1-Fe1)3@C.

[0067] Example 10

[0068] 1.212g3,3',4,4'-benzophenonecarboxylic acid dianhydride (1mol) and 0.822g p-phenylenediamine (2mol) were dissolved in 30mL DMF, recorded as solution A. 0.616g anhydrous ferric chloride (1mol) and 1.142g thioacetamide (4mol) were dissolved in 30mL DMF, recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 180℃ for 10h. After the reaction, the reaction liquid was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times respectively. Dry in a vacuum at 60℃. A dark brown powder can be obtained.

[0069] The dark brown powder obtained above was etched using 50% sulfuric acid.

[0070] The dark brown powder obtained above was placed in a crucible and calcined at 500 °C for 3 h with a heating rate of 5 °C / min to finally obtain sulfur-modified Fe-polymer-based self-assembled nanospheres, denoted as PI 10h -S1-Fe1@C.

[0071] Embodiment 11

[0072] 1.212g3,3',4,4'-dibenzophenonecarboxylic acid dianhydride (1mol) and 0.822g p-phenylenediamine (2mol) were dissolved in 30mL DMF, recorded as solution A. 0.616g anhydrous ferric chloride (1mol) and 1.142g thioacetamide (4mol) were dissolved in 30mL DMF, recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 180℃ for 8h. After the reaction, the reaction liquid was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times respectively. Dry in a vacuum at 60℃. A dark brown powder can be obtained.

[0073] The dark brown powder obtained above was etched using 50% sulfuric acid.

[0074] The dark brown powder obtained above was placed in a crucible and calcined at 500 °C for 3 h with a heating rate of 5 °C / min to finally obtain sulfur-modified Fe-polymer-based self-assembled nanospheres, denoted as PI 8h -S1-Fe1@C.

[0075] Example 12

[0076] 1.212g3,3',4,4'-dibenzophenonecarboxylic acid dianhydride (1mol) and 0.822g p-phenylenediamine (2mol) were dissolved in 30mL DMF, recorded as solution A. 0.616g anhydrous ferric chloride (1mol) and 1.142g thioacetamide (4mol) were dissolved in 30mL DMF, recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 180℃ for 6h. After the reaction, the reaction liquid was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times respectively. Dry in a vacuum at 60℃. A dark brown powder can be obtained.

[0077] The dark brown powder obtained above was etched using sulfuric acid with a concentration of 10%.

[0078] The dark brown powder obtained above was placed in a crucible and calcined at 500°C for 3 h with a heating rate of 5°C / min, and finally sulfur-modified Fe-polymer-based self-assembled nanospheres were obtained, which were recorded as 1PI-S1-Fe1@C.

[0079] Example 13

[0080] 1.212g3,3',4,4'-dibenzophenonecarboxylic acid dianhydride (1mol) and 0.822g p-phenylenediamine (2mol) were dissolved in 30mL DMF, recorded as solution A. 0.616g anhydrous ferric chloride (1mol) and 1.142g thioacetamide (4mol) were dissolved in 30mL DMF, recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 180℃ for 6h. After the reaction, the reaction liquid was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times respectively. Dry in a vacuum at 60℃. A dark brown powder can be obtained.

[0081] The dark brown powder obtained above was etched using sulfuric acid with a concentration of 60%.

[0082] The dark brown powder obtained above was placed in a crucible and calcined at 500°C for 3 h with a heating rate of 5°C / min to finally obtain sulfur-modified Fe-polymer-based self-assembled nanospheres, which were recorded as 2PI-S1-Fe1@C.

[0083] Embodiment 14

[0084] 1.212g3,3',4,4'-dibenzophenonecarboxylic acid dianhydride (1mol) and 0.822g p-phenylenediamine (2mol) were dissolved in 30mL DMF, recorded as solution A. 0.616g anhydrous ferric chloride (1mol) and 2.570g thioacetamide (9mol) were dissolved in 30mL DMF, recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 180℃ for 6h. After the reaction, the reaction liquid was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times respectively. Dry in a vacuum at 60℃. A dark brown powder can be obtained.

[0085] The dark brown powder obtained above was etched using 50% sulfuric acid.

[0086] The dark brown powder obtained above was placed in a crucible and calcined at 500°C for 3 h with a heating rate of 5°C / min, and finally sulfur-modified Fe-polymer-based self-assembled nanospheres were obtained, which were recorded as PI-S2-Fe3@C.

[0087] Embodiment 15

[0088] 1.212g3,3',4,4'-dibenzophenonecarboxylic acid dianhydride (1mol) and 0.822g p-phenylenediamine (2mol) were dissolved in 30mL DMF, recorded as solution A. 0.616g anhydrous ferric chloride (1mol) and 1.998g thioacetamide (7mol) were dissolved in 30mL DMF, recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 180℃ for 6h. After the reaction, the reaction liquid was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times respectively. Dry in a vacuum at 60℃. A dark brown powder can be obtained. 。

[0089] The dark brown powder obtained above was etched using 50% sulfuric acid.

[0090] The dark brown powder obtained above was placed in a crucible and calcined at 500°C for 3 h with a heating rate of 5°C / min, and finally sulfur-modified Fe-polymer-based self-assembled nanospheres were obtained, which were recorded as PI-S3-Fe4@C.

[0091] Example 16

[0092] 1.212g3,3',4,4'-dibenzophenonecarboxylic acid dianhydride (1mol) and 3.289g p-phenylenediamine (8mol) were dissolved in 30mL DMF, recorded as solution A. 0.616g anhydrous ferric chloride (1mol) and 1.142g thioacetamide (4mol) were dissolved in 30mL DMF, recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 180℃ for 6h. After the reaction, the reaction liquid was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times respectively. Dry in a vacuum at 60℃. A dark brown powder can be obtained.

[0093] The dark brown powder obtained above was etched using 50% sulfuric acid.

[0094] The dark brown powder obtained above was placed in a crucible and calcined at 500°C for 3 h with a heating rate of 5°C / min, and finally sulfur-modified Fe-polymer-based self-assembled nanospheres were obtained, which were recorded as PI'-S1-Fe1@C.

[0095] Embodiment 17

[0096] 0.829g of pyromellitic anhydride (1mol) and 0.822g of p-phenylenediamine (2mol) were dissolved in 30mL of DMF, which was recorded as solution A. 0.616g of anhydrous ferric chloride (1mol) and 1.142g of thioacetamide (4mol) were dissolved in 30mL of DMF, which was recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 180℃ for 6h. After the reaction, the reaction liquid was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times respectively. Vacuum dried at 60℃. A dark brown powder can be obtained.

[0097] The dark brown powder obtained above was etched using 50% sulfuric acid.

[0098] The dark brown powder obtained above was placed in a crucible and calcined at 500°C for 3 h with a heating rate of 5°C / min to finally obtain sulfur-modified Fe-polymer-based self-assembled nanospheres, which were recorded as PI / 1-S1-Fe1@C.

[0099] Embodiment 18

[0100] 1.212g3,3',4,4'-dibenzophenonecarboxylic acid dianhydride (1mol) and 0.822g o-phenylenediamine (2mol) were dissolved in 30mL DMF, recorded as solution A. 0.616g anhydrous ferric chloride (1mol) and 1.142g thioacetamide (4mol) were dissolved in 30mL DMF, recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 180℃ for 6h. After the reaction, the reaction liquid was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times respectively. Dry in a vacuum at 60℃. A dark brown powder can be obtained.

[0101] The dark brown powder obtained above was etched using 50% sulfuric acid.

[0102] The dark brown powder obtained above was placed in a crucible and calcined at 500°C for 3 h with a heating rate of 5°C / min to finally obtain sulfur-modified Fe-polymer-based self-assembled nanospheres, which were recorded as PI / 2-S1-Fe1@C.

[0103] Embodiment 19

[0104] 1.212g3,3',4,4'-dibenzophenonecarboxylic acid dianhydride (1mol) and 0.822gm-phenylenediamine (2mol) were dissolved in 30mL DMF, which was recorded as solution A. 0.616g anhydrous ferric chloride (1mol) and 1.142gthioacetamide (4mol) were dissolved in 30mL DMF, which was recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 180℃ for 6h. After the reaction, the reaction liquid was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times respectively. Dry in a vacuum at 60℃. A dark brown powder can be obtained.

[0105] The dark brown powder obtained above was etched using 50% sulfuric acid.

[0106] The dark brown powder obtained above was placed in a crucible and calcined at 500°C for 3 h with a heating rate of 5°C / min, and finally sulfur-modified Fe-polymer-based self-assembled nanospheres were obtained, which were recorded as PI / 3-S1-Fe1@C.

[0107] Embodiment 20

[0108] 1.212g3,3',4,4'-dibenzophenonecarboxylic acid dianhydride (1mol) and 0.822g p-phenylenediamine (2mol) were dissolved in 30mL acetone, which was recorded as solution A. 0.616g anhydrous ferric chloride (1mol) and 1.142g thioacetamide (4mol) were dissolved in 30mL acetone, which was recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 180℃ for 6h. After the reaction, the reaction liquid was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times respectively. Dry in a vacuum at 60℃. A dark brown powder can be obtained.

[0109] The dark brown powder obtained above was etched using 50% sulfuric acid.

[0110] The dark brown powder obtained above was placed in a crucible and calcined at 500°C for 3 h with a heating rate of 5°C / min to finally obtain sulfur-modified Fe-polymer-based self-assembled nanospheres, which were recorded as (PI-S1-Fe1)1@C.

[0111] Embodiment 21

[0112] 1.212g3,3',4,4'-benzophenonecarboxylic acid dianhydride (1mol) and 0.822g p-phenylenediamine (2mol) were dissolved in 30mL N-methylpyrrolidone. 0.616g anhydrous ferric chloride (1mol) and 1.142g thioacetamide (4mol) were dissolved in 30mL N-methylpyrrolidone, which was recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 180℃ for 6h. After the reaction, the reaction liquid was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times respectively. Dry in a vacuum at 60℃. A dark brown powder can be obtained.

[0113] The dark brown powder obtained above was etched using 50% sulfuric acid.

[0114] The dark brown powder obtained above was placed in a crucible and calcined at 500°C for 3 h with a heating rate of 5°C / min to finally obtain sulfur-modified Fe-polymer-based self-assembled nanospheres, which were recorded as (PI-S1-Fe1)2@C.

[0115] Comparative Example 1

[0116] 1.212g3,3',4,4'-dibenzophenonecarboxylic acid dianhydride (1mol) and 0.407g p-phenylenediamine (1mol) were dissolved in 30mL DMF, which was recorded as solution A. 0.616g anhydrous ferric chloride (1mol) and 1.142g thioacetamide (4mol) were dissolved in 30mL DMF, which was recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 180℃ for 6h. After the reaction, the reaction liquid was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times respectively. Dry in a vacuum at 60℃. A dark brown powder can be obtained.

[0117] The dark brown powder obtained above was etched using 50% sulfuric acid.

[0118] The dark brown powder obtained above was placed in a crucible and calcined at 500°C for 3 h with a heating rate of 5°C / min to form sulfur-modified Fe-polymer-based self-assembled nanosheets, denoted as 1(PI-S1-Fe1)@C.

[0119] Comparative Example 2

[0120] 1.212g3,3',4,4'-dibenzophenonecarboxylic acid dianhydride (1mol) and 3.659g p-phenylenediamine (9mol) were dissolved in 30mL DMF, recorded as solution A. 0.616g anhydrous ferric chloride (1mol) and 1.142g thioacetamide (4mol) were dissolved in 30mL DMF, recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 180℃ for 6h. After the reaction, the reaction liquid was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times respectively. Dry in a vacuum at 60℃. A dark brown powder can be obtained.

[0121] The dark brown powder obtained above was etched using 50% sulfuric acid.

[0122] The dark brown powder obtained above was placed in a crucible and calcined at 500°C for 3 h with a heating rate of 5°C / min to produce sulfur-modified Fe-polymer-based self-assembled nanosheets, denoted as 2(PI-S1-Fe1)@C.

[0123] Comparative Example 3

[0124] 1.212g3,3',4,4'-dibenzophenonecarboxylic acid dianhydride (1mol) and 4.066g p-phenylenediamine (10mol) were dissolved in 30mL DMF, recorded as solution A. 0.616g anhydrous ferric chloride (1mol) and 1.142g thioacetamide (4mol) were dissolved in 30mL DMF, recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 180℃ for 6h. After the reaction, the reaction liquid was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times respectively. Dry in a vacuum at 60℃. A dark brown powder can be obtained.

[0125] The dark brown powder obtained above was etched using 50% sulfuric acid.

[0126] The dark brown powder obtained above was placed in a crucible and calcined at 500°C for 3 h with a heating rate of 5°C / min to produce sulfur-modified Fe-polymer-based self-assembled nanosheets, denoted as 3(PI-S1-Fe1)@C.

[0127] Comparative Example 4

[0128] 1.212g3,3',4,4'-dibenzophenonecarboxylic acid dianhydride (1mol) and 0.822g p-phenylenediamine (2mol) were dissolved in 30mL DMF, recorded as solution A. 0.616g anhydrous ferric chloride (1mol) and 0.565g thioacetamide (2mol) were dissolved in 30mL DMF, recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 180℃ for 6h. After the reaction, the reaction liquid was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times respectively. Dry in a vacuum at 60℃. A dark brown powder can be obtained.

[0129] The dark brown powder obtained above was etched using 50% sulfuric acid.

[0130] The dark brown powder obtained above was placed in a crucible and calcined at 500°C for 3 h with a heating rate of 5°C / min to produce sulfur-modified Fe-polymer-based self-assembled nanosheets, denoted as 4(PI-S1-Fe1)@C.

[0131] Comparative Example 5

[0132] 1.212g3,3',4,4'-dibenzophenonecarboxylic acid dianhydride (1mol) and 0.822g p-phenylenediamine (2mol) were dissolved in 30mL DMF, which was recorded as solution A. 0.616g anhydrous ferric chloride (1mol) and 0.848g thioacetamide (3mol) were dissolved in 30mL DMF, which was recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 180℃ for 6h. After the reaction, the reaction liquid was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times respectively. Dry in a vacuum at 60℃. A dark brown powder can be obtained.

[0133] The dark brown powder obtained above was etched using 50% sulfuric acid.

[0134] The dark brown powder obtained above was placed in a crucible and calcined at 500°C for 3 h with a heating rate of 5°C / min to produce sulfur-modified Fe-polymer-based self-assembled nanosheets, denoted as 5(PI-S1-Fe1)@C.

[0135] Comparative Example 6

[0136] 1.212g3,3',4,4'-dibenzophenonecarboxylic acid dianhydride (1mol) and 0.822g p-phenylenediamine (2mol) were dissolved in 30mL DMF, recorded as solution A. 0.616g anhydrous ferric chloride (1mol) and 2.825g thioacetamide (10mol) were dissolved in 30mL DMF, recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 180℃ for 6h. After the reaction, the reaction liquid was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times respectively. Dry in a vacuum at 60℃. A dark brown powder can be obtained.

[0137] The dark brown powder obtained above was etched using 50% sulfuric acid.

[0138] The dark brown powder obtained above was placed in a crucible and calcined at 500°C for 3 h with a heating rate of 5°C / min to produce sulfur-modified Fe-polymer-based self-assembled nanosheets, denoted as 6(PI-S1-Fe1)@C.

[0139] Comparative Example 7

[0140] 1.212g3,3',4,4'-benzophenonecarboxylic acid dianhydride (1mol) and 0.822g p-phenylenediamine (2mol) were dissolved in 30mL DMF, which was recorded as solution A. 0.616g anhydrous ferric chloride (1mol) and 3.108g thioacetamide (11mol) were dissolved in 30mL DMF, which was recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 180℃ for 6h. After the reaction, the reaction liquid was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times respectively. Dry in a vacuum at 60℃. A dark brown powder can be obtained.

[0141] The dark brown powder obtained above was etched using 50% sulfuric acid.

[0142] The dark brown powder obtained above was placed in a crucible and calcined at 500°C for 3 h with a heating rate of 5°C / min to produce sulfur-modified Fe-polymer-based self-assembled nanosheets, denoted as 7(PI-S1-Fe1)@C.

[0143] Comparative Example 8

[0144] 1.212g3,3',4,4'-dibenzophenonecarboxylic acid dianhydride (1mol) and 0.822g p-phenylenediamine (2mol) were dissolved in 30mL DMF, recorded as solution A. 0.616g anhydrous ferric chloride (1mol) and 1.142g thioacetamide (4mol) were dissolved in 30mL DMF, recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 180℃ for 6h. After the reaction, the reaction liquid was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times respectively. Dry in a vacuum at 60℃. A dark brown powder can be obtained.

[0145] The dark brown powder obtained above was etched using 5% sulfuric acid.

[0146] The dark brown powder obtained above was placed in a crucible and calcined at 500°C for 3 h with a heating rate of 5°C / min to produce sulfur-modified Fe-polymer-based self-assembled nanosheets, denoted as 1(1PI-S1-Fe1)@C.

[0147] Comparative Example 9

[0148] 1.212g3,3',4,4'-dibenzophenonecarboxylic acid dianhydride (1mol) and 0.822g p-phenylenediamine (2mol) were dissolved in 30mL DMF, recorded as solution A. 0.616g anhydrous ferric chloride (1mol) and 1.142g thioacetamide (4mol) were dissolved in 30mL DMF, recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 180℃ for 6h. After the reaction, the reaction liquid was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times respectively. Dry in a vacuum at 60℃. A dark brown powder can be obtained.

[0149] The dark brown powder obtained above was etched using sulfuric acid with a concentration of 70%.

[0150] The dark brown powder obtained above was placed in a crucible and calcined at 500°C for 3 h with a heating rate of 5°C / min to produce sulfur-modified Fe-polymer-based self-assembled nanosheets, denoted as 2(1PI-S1-Fe1)@C.

[0151] Comparative Example 10

[0152] 1.212g3,3',4,4'-dibenzophenonecarboxylic acid dianhydride (1mol) and 0.822g p-phenylenediamine (2mol) were dissolved in 30mL DMF, recorded as solution A. 0.616g anhydrous ferric chloride (1mol) and 1.142g thioacetamide (4mol) were dissolved in 30mL DMF, recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 180℃ for 6h. After the reaction, the reaction liquid was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times respectively. Dry in a vacuum at 60℃. A dark brown powder can be obtained.

[0153] The dark brown powder obtained above was etched using sulfuric acid with a concentration of 80%.

[0154] The dark brown powder obtained above was placed in a crucible and calcined at 500°C for 3 h with a heating rate of 5°C / min to produce sulfur-modified Fe-polymer-based self-assembled nanosheets, denoted as 3(1PI-S1-Fe1)@C.

[0155] Comparative Example 11

[0156] 1.212g3,3',4,4'-dibenzophenonecarboxylic acid dianhydride (1mol) and 0.822g p-phenylenediamine (2mol) were dissolved in 30mL DMF, recorded as solution A. 0.616g anhydrous ferric chloride (1mol) and 1.142g thioacetamide (4mol) were dissolved in 30mL DMF, recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 140℃ for 6h. After the reaction, the reaction liquid was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times respectively. Vacuum dried at 60℃. A dark brown powder can be obtained.

[0157] The dark brown powder obtained above was etched using 50% sulfuric acid.

[0158] The dark brown powder obtained above was placed in a crucible and calcined at 500°C for 3 h with a heating rate of 5°C / min to produce sulfur-modified Fe-polymer-based self-assembled nanosheets, denoted as 1(PI-S1-Fe1)1@C.

[0159] Comparative Example 12

[0160] 1.212g3,3',4,4'-dibenzophenonecarboxylic acid dianhydride (1mol) and 0.822g p-phenylenediamine (2mol) were dissolved in 30mL DMF, which was recorded as solution A. 0.616g anhydrous ferric chloride (1mol) and 1.142g thioacetamide (4mol) were dissolved in 30mL DMF, which was recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 180℃ for 4h. After the reaction, the reaction liquid was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times respectively. Dry in a vacuum at 60℃. A dark brown powder can be obtained.

[0161] The dark brown powder obtained above was etched using 50% sulfuric acid.

[0162] The dark brown powder obtained above was placed in a crucible and calcined at 500 °C for 3 h with a heating rate of 5 °C / min. Sulfur-modified Fe-polymer-based self-assembled nanosheets were prepared, denoted as PI. 4h -S1-Fe1@C.

[0163] Comparative Example 13

[0164] 1.212g3,3',4,4'-dibenzophenonecarboxylic acid dianhydride (1mol) and 0.822g p-phenylenediamine (2mol) were dissolved in 30mL DMF, which was recorded as solution A. 0.616g anhydrous ferric chloride (1mol) and 1.142g thioacetamide (4mol) were dissolved in 30mL DMF, which was recorded as solution B. Solution B was added dropwise to solution A and ultrasonicated for 10min to obtain a uniform solution. At room temperature, the stirring speed was 500r / min and stirred until the reaction was complete to form a uniform polymer solution. Put it into a reactor and react at 180℃ for 12h. After the reaction, the reaction liquid was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times respectively. Dry in a vacuum at 60℃. A dark brown powder can be obtained.

[0165] The dark brown powder obtained above was etched using 50% sulfuric acid.

[0166] The dark brown powder obtained above was placed in a crucible and calcined at 500 °C for 3 h with a heating rate of 5 °C / min. Sulfur-modified Fe-polymer-based self-assembled nanosheets were prepared, denoted as PI. 12h -S1-Fe1@C.

[0167] The catalysts prepared in Examples 1 to 21 and Comparative Examples 1 to 13 were subjected to performance tests to test their catalytic performance in photo-Fenton degradation of dyes. The catalytic performance of the catalysts and their ability to degrade organic pollutants in wastewater were analyzed by calculating the decolorization rate of the dyes, as shown in Table 1.

[0168] The specific steps of the experiment are as follows: first, prepare 100 mL of 4BS dye solution with a concentration of 50 mg / L, then weigh 0.05-1.0 g of catalyst and add it to the dye solution, place the solution on an oscillator, and before the photocatalytic degradation experiment, stir the reaction solution without turning on the light for 30 minutes to achieve the adsorption equilibrium of the catalyst; turn on the light and add hydrogen peroxide, and start the degradation experiment with the light on. The degradation time is 150 minutes, and samples are taken at regular intervals, and their absorbance is tested after filtering.

[0169] First, 100 mL of p-methamphetamine with a concentration of 10 ng / L was prepared, and then 0.05-1.0 g of catalyst was weighed and added to the solution. The solution was placed on an oscillator and adsorbed for 30 min. A sample was taken at regular intervals and its absorbance was tested after filtration. (Experimental test of Example 5)

[0170] First, 100 mL of ketamine with a concentration of 100 ng / L was prepared, and then 0.05-1.0 g of catalyst was weighed and added to the solution. The solution was placed on an oscillator and adsorbed for 30 minutes. Samples were taken at regular intervals, and the absorbance was tested after filtration. (Experimental test of Example 6)

[0171] There is a positive correlation between absorbance, concentration and optical path length. The Lambert-Beer law can be expressed by formula (1-1)

[0172] A=εbc (1-1)

[0173] In the above formula, A is absorbance; usually A t represents the absorbance of each sampling, and t is a natural number, indicating the sampling sequence number;

[0174] ε——molar absorption coefficient;

[0175] b——liquid layer thickness, cm;

[0176] c——Concentration of light-absorbing substance, mol·L -1 . Usually C t represents the concentration of the absorbing substance measured in each sampling, and t is a natural number, indicating the sampling sequence number;

[0177] The contamination rate of macromolecular pollutants is calculated according to formula (1-2):

[0178] η=C t / C0 (1-2)

[0179] In the above formula, η is the pollution rate;

[0180] C——Concentration of pollutant at a certain moment of reaction, mg·L -1 ;

[0181] C0——Concentration of pollutant at the initial moment, mg·L -1 .

[0182] Take Example 1 as an example for calculation: In formula (1-1), ε and b are fixed values ​​and can offset each other in the calculation, so the absorbance of A is approximately equal to the concentration of the absorbing substance C.

[0183] A absorbance is measured by UV spectrophotometer, A0≈C0=1.251

[0184] A t ≈C t (t represents the order number of each sampling) = 0.200

[0185] Therefore, the ability of the catalyst to degrade organic pollutants in wastewater is calculated by decolorization rate: decolorization rate = 1-C t / C0=1-0.200 / 1.251*100%=84%

[0186] Table 1:

[0187]

[0188]

Claims

1. A sulfur-modified Fe-polymer-based self-assembled nanosphere, characterized in that: The sulfur-modified Fe-polymer-based self-assembled nanospheres are prepared from anhydride, phenylenediamine, iron salt, and thioacetamide in a molar ratio of 1:2-8:1:4-9, and the preparation method is as follows: (1) dissolving the acid anhydride and the phenylenediamine in an organic solvent A to obtain a solution A, dissolving the iron salt and the thioacetamide in an organic solvent B to obtain a solution B, adding the solution B dropwise to the solution A, and then mixing by ultrasonication to obtain a mixed solution; the mass ratio of the acid anhydride to the organic solvent A is 1:18-51, and the mass ratio of the iron salt to the organic solvent B is 1:18-51; (2) reacting the mixed solution at a temperature of 160-200° C. for 6-10 hours to obtain a reaction solution; (3) centrifuging the reaction solution in step (2), removing the liquid, washing with DMF and methanol respectively, and drying to obtain a dark brown powder; (4) etching the dark brown powder prepared in step (3) with a sulfuric acid aqueous solution having a mass concentration of 10% to 60% to obtain an etched dark brown powder; (5) The dark brown powder etched with sulfuric acid in step (4) is placed in a crucible and calcined at 400-600° C. for 2-4 h to obtain the sulfur-modified Fe-polymer-based self-assembled nanospheres, with the calcination heating rate being 2-5° C. / min.

2. The sulfur-modified Fe-polymer-based self-assembled nanospheres according to claim 1, characterized in that: The acid anhydride is one or more of pyromellitic dianhydride and 3,3',4,4'-dibenzophenonecarboxylic dianhydride.

3. The sulfur-modified Fe-polymer-based self-assembled nanospheres according to claim 1, characterized in that The phenylenediamine is one or more of p-phenylenediamine, o-phenylenediamine or m-phenylenediamine.

4. The sulfur-modified Fe-polymer-based self-assembled nanospheres according to claim 1, characterized in that: The iron salt is an organic iron salt or an inorganic iron salt. The organic iron salt is ferric acetylacetonate, and the inorganic iron salt is one or more of ferric chloride and ferric nitrate.

5. The sulfur-modified Fe-polymer-based self-assembled nanospheres according to any one of claims 2 to 4, characterized in that: The molar ratio of the acid anhydride, phenylenediamine, iron salt and thioacetamide is 1:2:1:

4.

6. The sulfur-modified Fe-polymer-based self-assembled nanospheres according to claim 1, characterized in that: The reaction in step (2) is carried out at 180° C. for 6 hours to obtain a reaction solution.

7. The sulfur-modified Fe-polymer-based self-assembled nanospheres according to claim 1, characterized in that: The drying in step (3) is performed at 60° C. in vacuum for 12 hours.

8. The sulfur-modified Fe-polymer-based self-assembled nanospheres according to claim 1, characterized in that: The mass concentration of the aqueous sulfuric acid solution in step (4) is 50%.

9. Use of the sulfur-modified Fe-polymer-based self-assembled nanospheres as claimed in claim 1 as a degradation catalyst in degrading organic pollutants in wastewater.

10. The use according to claim 9, characterized in that The application method is as follows: adding 0.05-1.0% sulfur-modified Fe-polymer-based self-assembled nanospheres as catalysts into wastewater containing organic pollutants, oscillating the reaction for 30-60 minutes, and then adding hydrogen peroxide under illumination to continue the reaction until it is complete.

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