Sulfur-modified fe-polymer-based self-assembled nanospheres and applications thereof

Abstract

The application discloses a kind of sulfur modified Fe-polymer base self-assembled nanospheres, the sulfur modified Fe-polymer base self-assembled nanospheres are prepared by acid anhydride, phenylenediamine, iron salt, thioacetamide according to the mass ratio 1:2-8:1:4-9, by polymerization, product is dried to obtain black brown powder, then using 10%-60% sulfuric acid aqueous solution with mass concentration is etched, after etching, it is placed in crucible, and is calcined at 400~600 DEG C for 2~4h, to obtain target product.N-H bond and iron element are introduced into nanosphere in the application, the active site of nanosphere is increased, the number and volume of holes on nanosphere are increased by sulfuric acid etching, so as to increase the contact area of nanosphere and reactant, and then improve the catalytic efficiency and stability.The preparation method of the application is simple in operation, low in cost and less in waste.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of photocatalysis, and particularly relates to a sulfur-modified Fe-polymer-based self-assembled nanosphere and application thereof as a catalyst for degrading organic pollutants in wastewater. BACKGROUND

[0002] With the rapid development of science and industry, wastewater discharge is one of the more intractable problems in water pollution, and a large amount of wastewater is discharged into rivers, lakes and seas, including medical wastewater, pesticide wastewater, biological wastewater, printing and dyeing wastewater and the like, which usually contains a large amount of organic matter and metal ions. Organic pollutants in water have complex and diverse structures and are difficult to degrade, and have biological hazards such as toxicity, teratogenicity and mutagenicity, so efficient and convenient water treatment technology is urgently needed for pollution control.

[0003] Photocatalysis technology provides an efficient and environmentally friendly solution for removing these organic pollutants. In order to find a non-noble metal catalyst that is low in price, has good catalytic effect and causes little environmental pollution, many researchers have turned their attention to the study of porous carbon catalysts. Porous carbon nanoflower is a kind of spherical nanocarbon material with rich interpenetrating or closed pore structure characteristics, mainly used in photoelectric catalytic water treatment materials. This technology is a new type of wastewater treatment technology and does not produce secondary pollution. Porous carbon materials continuously expand their application fields by adjusting pore size, surface area and doping other elements, and are widely used in research and production fields such as adsorption, catalysis and energy storage. Porous carbon nanospheres have spherical morphology, rich and controllable internal pore structure and easily modified surface groups, and can play an important role in heterogeneous catalytic reactions. Doping metal elements into nanoflower spheres can easily cause the loss and shedding of active sites. Therefore, the present application aims to find a suitable product that can make metal active sites grow uniformly inside the nanosphere, greatly improve the catalytic stability of the nanosphere, and synthesize a metal-organic nanosheet assembled into a spherical catalyst with simple process, less waste and good environmental friendliness, which can effectively catalyze and degrade organic pollutants in wastewater. SUMMARY

[0004] In order to overcome the shortcomings of the prior art, the present application 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, and the preparation method comprises the following steps:

[0006] (1) the acid anhydride and the phenylenediamine are dissolved in an organic solvent A to obtain solution A, the iron salt and the thioacetamide are dissolved in an organic solvent B to obtain solution B, the solution B is added dropwise into the solution B, and the mixture is mixed by ultrasonic wave 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; the organic solvent A is DMF, and the organic solvent B is DMF;

[0007] (2) the mixed solution is reacted at a temperature of 160-200 ℃ for 6-10 hours to obtain a reaction liquid.

[0008] (3) the reaction liquid in step (2) is centrifuged, the liquid is removed, and the obtained residue is washed with DMF and methanol respectively, filtered, and dried to obtain a black-brown powder.

[0009] (4) the black-brown powder obtained in step (3) is etched with a sulfuric acid aqueous solution with a mass concentration of 10%-60% to obtain an etched black-brown powder.

[0010] (5) the etched black-brown powder in step (4) is placed in a crucible and calcined at 400-600 ℃ for 2-4 hours to obtain the sulfur-modified Fe-polymer-based self-assembled nanospheres, and the heating rate of the calcination is 2-5 ℃ / min. Specifically, the calcination in step (5) is carried out at 500 ℃ for 3 hours, and the heating rate is 5 ℃ / min.

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

[0012] Further, the phenylenediamine is one or more of p-phenylenediamine, o-phenylenediamine and m-phenylenediamine.

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

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

[0015] Further, the reaction in step (2) is carried out at a temperature of 180 ℃ for 6 hours to obtain a reaction liquid.

[0016] Further, the drying in step (3) is carried out at 60 ℃ under vacuum for 12 hours.

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

[0018] The application also relates to application of the sulfur-modified Fe-polymer-based self-assembled nanospheres to degradation of organic pollutants in wastewater as a catalyst.

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

[0020] The application introduces N-H bonds and iron elements into the nanospheres by copolymerization of anhydride, phenylenediamine, iron salt and thioacetamide and then sulfuric acid etching and calcination, increases the active sites of the nanospheres, improves the catalytic activity and catalytic stability of the nanospheres, increases the number and volume of the pores on the nanospheres through sulfuric acid etching, thereby increasing the contact area of the nanospheres and reactants and improving the catalytic efficiency, and the preparation method of the nanospheres is simple in operation, low in cost and small in waste material generation. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 A scanning electron microscope image of the sulfur-modified Fe-polymer-based self-assembled nanospheres obtained in Example 3 of the application.

[0022] Figure 2 An adsorption amount curve of the sulfur-modified Fe-polymer-based self-assembled nanospheres obtained in Example 5 of the application for adsorbing para-methamphetamine.

[0023] Figure 3 An adsorption amount curve of the sulfur-modified Fe-polymer-based self-assembled nanospheres obtained in Example 6 of the application for adsorbing ketamine. DETAILED DESCRIPTION

[0024] The application will be further described below through specific examples, but the protection scope of the application is not limited to this.

[0025] Example 1

[0026] 1. 1.212 g of 3,3',4,4'-benzophenone dicarboxylic dianhydride (1 mol) and 0.822 g of p-phenylenediamine (2 mol) were dissolved in 30 mL of DMF, denoted as solution A. 0.616 g of anhydrous ferric chloride (1 mol) and 1.142 g of thioacetamide (4 mol) were dissolved in 30 mL of DMF, denoted as solution B. Solution B was added dropwise to solution A, and after ultrasonic treatment for 10 min, a uniform solution was obtained. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, and a uniform polymer solution was formed. The solution was placed in a reaction kettle and reacted at 180 °C for 6 h. After the reaction was completed, the reaction solution was centrifuged, and the liquid was removed and washed three times with DMF and methanol, respectively. Vacuum drying was performed at 60 °C. A black-brown powder was obtained.

[0027] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 50%.

[0028] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 50%.

[0029] Example 2

[0030] 1. 1.212 g of 3,3',4,4'-benzophenone dicarboxylic dianhydride (1 mol) and 0.822 g of p-phenylenediamine (2 mol) were dissolved in 30 mL of DMF, denoted as solution A. 1.535 g of ferric nitrate (1 mol) and 1.142 g of thioacetamide (4 mol) were dissolved in 30 mL of DMF, denoted as solution B. Solution B was added dropwise to solution A, and after ultrasonic treatment for 10 min, a uniform solution was obtained. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, and a uniform polymer solution was formed. The solution was placed in a reaction kettle and reacted at 180 °C for 6 h. After the reaction was completed, the reaction solution was centrifuged, and the liquid was removed and washed three times with DMF and methanol, respectively. Vacuum drying was performed at 60 °C. A black-brown powder was obtained.

[0031] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 50%.

[0032] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 50%.

[0033] Example 3

[0034] 1.212 g of 3,3',4,4'-benzophenone dicarboxylic dianhydride (1 mol) and 0.822 g of p-phenylenediamine (2 mol) were dissolved in 30 mL of DMF, denoted as solution A. 0.308 g of anhydrous ferric chloride (0.5 mol) and 0.767 g of ferric nitrate (0.5 mol) and 1.142 g of thioacetamide (4 mol) were dissolved in 30 mL of DMF, denoted as solution B. Solution B was added dropwise to solution A, and a uniform solution was obtained after ultrasonic treatment for 10 min. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, and a uniform polymer solution was formed. The reaction was carried out in a reaction kettle at 180 °C for 6 h. After the reaction was completed, the reaction solution was centrifuged, and the liquid was removed and washed with DMF and methanol three times, respectively. Vacuum drying was carried out at 60 °C. A black-brown powder was obtained.

[0035] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 50%.

[0036] The black-brown powder obtained above was placed in a crucible and calcined at 500 °C for 3 h at a heating rate of 5 °C / min, and finally sulfur-modified Fe-polymer-based self-assembled nanospheres were obtained, denoted as PI-S1-Fe1 / Fe2@C.

[0037] The scanning electron microscope image is shown in Figure 1. Figure 1

[0038] Example 4

[0039] 1.212 g of 3,3',4,4'-benzophenone dicarboxylic dianhydride (1 mol) and 0.822 g of p-phenylenediamine (2 mol) were dissolved in 30 mL of DMF, denoted as solution A. 1.342 g of iron acetylacetonate (1 mol) and 1.142 g of thioacetamide (4 mol) were dissolved in 30 mL of DMF, denoted as solution B. Solution B was added dropwise to solution A, and a uniform solution was obtained after ultrasonic treatment for 10 min. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, and a uniform polymer solution was formed. The reaction was carried out in a reaction kettle at 180 °C for 6 h. After the reaction was completed, the reaction solution was centrifuged, and the liquid was removed and washed with DMF and methanol three times, respectively. Vacuum drying was carried out at 60 °C. A black-brown powder was obtained.

[0040] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 50%.

[0041] The black-brown powder obtained above was placed in a crucible and calcined at 500 °C for 3 h at a heating rate of 5 °C / min, and finally sulfur-modified Fe-polymer-based self-assembled nanospheres were obtained, denoted as PI-S1-FA@C.

[0042] Example 5: (adsorption 1)

[0043] 1.212 g of 3,3',4,4'-benzophenone dicarboxylic dianhydride (1 mol) and 0.822 g of p-phenylenediamine (2 mol) were dissolved in 30 mL of DMF, denoted as solution A. 0.308 g of anhydrous ferric chloride (0.5 mol) and 0.767 g of ferric nitrate (0.5 mol) and 1.142 g of thioacetamide (4 mol) were dissolved in 30 mL of DMF, denoted as solution B. Solution B was added dropwise to solution A, and a uniform solution was obtained after ultrasonic treatment for 10 min. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, and a uniform polymer solution was formed. The reaction was carried out in a reaction kettle at 180 °C for 6 h. After the reaction was completed, the reaction solution was centrifuged, and the liquid was removed and washed three times with DMF and methanol, respectively. Vacuum drying was performed at 60 °C. A black-brown powder was obtained.

[0044] The black-brown powder obtained above was etched with sulfuric acid with a concentration of 50%.

[0045] The black-brown powder obtained above was placed in a crucible and calcined at 500 °C for 3 h at a heating rate of 5 °C / min, and finally a sulfur-modified Fe-polymer-based self-assembled nanosphere was obtained, denoted as PI-S1-Fe1 / Fe2@C (adsorption 1).

[0046] The final application was the adsorption of 10 ng / L of p-methylamphetamine within 30 min, and the adsorption amount curve of p-methylamphetamine is shown in FIG. 6. Figure 2 .

[0047] Example 6: (adsorption 2)

[0048] 1.212 g of 3,3',4,4'-benzophenone dicarboxylic dianhydride (1 mol) and 0.822 g of p-phenylenediamine (2 mol) were dissolved in 30 mL of DMF, denoted as solution A. 0.308 g of anhydrous ferric chloride (0.5 mol) and 0.767 g of ferric nitrate (0.5 mol) and 1.142 g of thioacetamide (4 mol) were dissolved in 30 mL of DMF, denoted as solution B. Solution B was added dropwise to solution A, and a uniform solution was obtained after ultrasonic treatment for 10 min. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, and a uniform polymer solution was formed. The reaction was carried out in a reaction kettle at 180 °C for 6 h. After the reaction was completed, the reaction solution was centrifuged, and the liquid was removed and washed three times with DMF and methanol, respectively. Vacuum drying was performed at 60 °C. A black-brown powder was obtained.

[0049] The black-brown powder obtained above was etched with sulfuric acid with a concentration of 50%.

[0050] The black-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, denoted as PI-S1-Fe1 / Fe2@C (adsorbed 2).

[0051] The last application was the adsorption of 100 ng / L of ketamine within 30 min, and the adsorption amount curve of ketamine adsorbed by the sulfur-modified Fe-polymer-based self-assembled nanospheres is shown in FIG. 6. Figure 3 .

[0052] Example 7

[0053] 1.212 g of 3,3',4,4'-benzophenone dicarboxylic dianhydride (1 mol) and 0.822 g of p-phenylenediamine (2 mol) were dissolved in 30 mL of DMF, denoted as solution A. 0.616 g of anhydrous ferric chloride (1 mol) and 1.142 g of thioacetamide (4 mol) were dissolved in 30 mL of DMF, denoted as solution B. Solution B was added dropwise to solution A, and a uniform solution was obtained after ultrasonic treatment for 10 min. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, and a uniform polymer solution was formed. The reaction was carried out in a reaction kettle at 160 °C for 6 h. After the reaction was completed, the reaction solution was centrifuged, and the liquid was removed and washed with DMF and methanol three times, respectively. Vacuum drying was carried out at 60 °C. A black-brown powder was obtained.

[0054] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 50 %.

[0055] The black-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, denoted as (PI-S1-Fe1)1@C.

[0056] Example 8

[0057] 1.212 g of 3,3',4,4'-benzophenone dicarboxylic dianhydride (1 mol) and 0.822 g of p-phenylenediamine (2 mol) were dissolved in 30 mL of DMF, denoted as solution A. 0.616 g of anhydrous ferric chloride (1 mol) and 1.142 g of thioacetamide (4 mol) were dissolved in 30 mL of DMF, denoted as solution B. Solution B was added dropwise to solution A, and a uniform solution was obtained after ultrasonic treatment for 10 min. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, and a uniform polymer solution was formed. The reaction was carried out in a reaction kettle at 200 °C for 6 h. After the reaction was completed, the reaction solution was washed with DMF and methanol three times, respectively. Vacuum drying was carried out at 60 °C. A black-brown powder was obtained.

[0058] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 50%.

[0059] The black-brown powder obtained above was placed in a crucible and calcined at 500 °C for 3 h with a temperature increase rate of 5 °C / min, and finally sulfur-modified Fe-polymer-based self-assembled nanospheres were obtained, denoted as (PI-S1-Fe1)2@C.

[0060] Example 9

[0061] 1.212 g of 3,3',4,4'-benzophenone dicarboxylic dianhydride (1 mol) and 0.822 g of p-phenylenediamine (2 mol) were dissolved in 30 mL of DMF, denoted as solution A. 0.616 g of anhydrous ferric chloride (1 mol) and 1.142 g of thioacetamide (4 mol) were dissolved in 30 mL of DMF, denoted as solution B. Solution B was added dropwise to solution A, and a uniform solution was obtained after ultrasonic treatment for 10 min. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, and a uniform polymer solution was formed. The solution was placed in a reaction kettle and reacted at 170 °C for 6 h. After the reaction was completed, the reaction solution was centrifuged, and the liquid was removed and washed three times with DMF and methanol, respectively. Vacuum drying was performed at 60 °C. A black-brown powder was obtained.

[0062] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 50%.

[0063] The black-brown powder obtained above was placed in a crucible and calcined at 500 °C for 3 h with a temperature increase rate of 5 °C / min, and finally sulfur-modified Fe-polymer-based self-assembled nanospheres were obtained, denoted as (PI-S1-Fe1)3@C.

[0064] Example 10

[0065] 1.212 g of 3,3',4,4'-benzophenone dicarboxylic dianhydride (1 mol) and 0.822 g of p-phenylenediamine (2 mol) were dissolved in 30 mL of DMF, denoted as solution A. 0.616 g of anhydrous ferric chloride (1 mol) and 1.142 g of thioacetamide (4 mol) were dissolved in 30 mL of DMF, denoted as solution B. Solution B was added dropwise to solution A, and a uniform solution was obtained after ultrasonic treatment for 10 min. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, and a uniform polymer solution was formed. The solution was placed in a reaction kettle and reacted at 180 °C for 10 h. After the reaction was completed, the reaction solution was centrifuged, and the liquid was removed and washed three times with DMF and methanol, respectively. Vacuum drying was performed at 60 °C. A black-brown powder was obtained.

[0066] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 50%.

[0067] The black-brown powder obtained above was placed in a crucible and calcined at 500 °C for 3 h with a temperature rising rate of 5 °C / min, and finally sulfur-modified Fe-polymer-based self-assembled nanospheres were obtained, denoted as PI 10 h -S1-Fe1@C.

[0068] Example 11

[0069] 1.212 g of 3,3',4,4'-benzophenone dicarboxylic dianhydride (1 mol) and 0.822 g of p-phenylenediamine (2 mol) were dissolved in 30 mL of DMF, denoted as solution A. 0.616 g of anhydrous ferric chloride (1 mol) and 1.142 g of thioacetamide (4 mol) were dissolved in 30 mL of DMF, denoted as solution B. Solution B was added dropwise to solution A, and a uniform solution was obtained after ultrasonic treatment for 10 min. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, and a uniform polymer solution was formed. The reaction was carried out in a reaction kettle at 180 °C for 8 h. After the reaction was completed, the reaction solution was centrifuged, and the liquid was removed and washed with DMF and methanol three times, respectively. Vacuum drying was carried out at 60 °C. A black-brown powder was obtained.

[0070] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 10%.

[0071] The black-brown powder obtained above was placed in a crucible and calcined at 500 °C for 3 h with a temperature rising rate of 5 °C / min, and finally sulfur-modified Fe-polymer-based self-assembled nanospheres were obtained, denoted as PI 8 h -S1-Fe1@C.

[0072] Example 12

[0073] 1.212 g of 3,3',4,4'-benzophenone dicarboxylic dianhydride (1 mol) and 0.822 g of p-phenylenediamine (2 mol) were dissolved in 30 mL of DMF, denoted as solution A. 0.616 g of anhydrous ferric chloride (1 mol) and 1.142 g of thioacetamide (4 mol) were dissolved in 30 mL of DMF, denoted as solution B. Solution B was added dropwise to solution A, and a uniform solution was obtained after ultrasonic treatment for 10 min. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, and a uniform polymer solution was formed. The reaction was carried out in a reaction kettle at 180 °C for 6 h. After the reaction was completed, the reaction solution was centrifuged, and the liquid was removed and washed with DMF and methanol three times, respectively. Vacuum drying was carried out at 60 °C. A black-brown powder was obtained.

[0074] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 10%.

[0075] The black-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, denoted as 1PI-S1-Fe1@C.

[0076] Example 13

[0077] 1.212 g of 3,3',4,4'-benzophenone dicarboxylic dianhydride (1 mol) and 0.822 g of p-phenylenediamine (2 mol) were dissolved in 30 mL of DMF, denoted as solution A. 0.616 g of anhydrous ferric chloride (1 mol) and 1.142 g of thioacetamide (4 mol) were dissolved in 30 mL of DMF, denoted as solution B. Solution B was added dropwise to solution A, and a uniform solution was obtained after ultrasonic treatment for 10 min. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, and a uniform polymer solution was formed. The reaction was carried out in a reaction kettle at 180 °C for 6 h. After the reaction was completed, the reaction solution was centrifuged, and the liquid was removed and washed with DMF and methanol three times, respectively. Vacuum drying was carried out at 60 °C. A black-brown powder was obtained.

[0078] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 60%.

[0079] The black-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, denoted as 2PI-S1-Fe1@C.

[0080] Example 14

[0081] 1.212 g of 3,3',4,4'-benzophenone dicarboxylic dianhydride (1 mol) and 0.822 g of p-phenylenediamine (2 mol) were dissolved in 30 mL of DMF, denoted as solution A. 0.616 g of anhydrous ferric chloride (1 mol) and 2.570 g of thioacetamide (9 mol) were dissolved in 30 mL of DMF, denoted as solution B. Solution B was added dropwise to solution A, and a uniform solution was obtained after ultrasonic treatment for 10 min. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, and a uniform polymer solution was formed. The reaction was carried out in a reaction kettle at 180 °C for 6 h. After the reaction was completed, the reaction solution was centrifuged, and the liquid was removed and washed with DMF and methanol three times, respectively. Vacuum drying was carried out at 60 °C. A black-brown powder was obtained.

[0082] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 50%.

[0083] The black-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 PI-S2-Fe3@C were obtained.

[0084] Example 15

[0085] 1.212 g of 3,3',4,4'-benzophenone dicarboxylic dianhydride (1 mol) and 0.822 g of p-phenylenediamine (2 mol) were dissolved in 30 mL of DMF, denoted as solution A. 0.616 g of anhydrous ferric chloride (1 mol) and 1.998 g of thioacetamide (7 mol) were dissolved in 30 mL of DMF, denoted as solution B. Solution B was added dropwise to solution A, and a uniform solution was obtained after ultrasonic treatment for 10 min. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, and a uniform polymer solution was formed. The reaction was carried out in a reaction kettle at 180 °C for 6 h. After the reaction was completed, the reaction solution was centrifuged, and the liquid was removed and washed with DMF and methanol three times, respectively. Vacuum drying was carried out at 60 °C. A black-brown powder was obtained. 。

[0086] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 50%.

[0087] The black-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 PI-S3-Fe4@C were obtained.

[0088] Example 16

[0089] 1.212 g of 3,3',4,4'-benzophenone dicarboxylic dianhydride (1 mol) and 3.289 g of p-phenylenediamine (8 mol) were dissolved in 30 mL of DMF, denoted as solution A. 0.616 g of anhydrous ferric chloride (1 mol) and 1.142 g of thioacetamide (4 mol) were dissolved in 30 mL of DMF, denoted as solution B. Solution B was added dropwise to solution A, and a uniform solution was obtained after ultrasonic treatment for 10 min. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, and a uniform polymer solution was formed. The reaction was carried out in a reaction kettle at 180 °C for 6 h. After the reaction was completed, the reaction solution was centrifuged, and the liquid was removed and washed with DMF and methanol three times, respectively. Vacuum drying was carried out at 60 °C. A black-brown powder was obtained.

[0090] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 50%.

[0091] The black-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 PI’-S1-Fe1@C were obtained.

[0092] Example 17

[0093] 0.829 g of pyromellitic dianhydride (1 mol) and 0.822 g of p-phenylenediamine (2 mol) were dissolved in 30 mL of DMF, denoted as solution A. 0.616 g of anhydrous ferric chloride (1 mol) and 1.142 g of thioacetamide (4 mol) were dissolved in 30 mL of DMF, denoted as solution B. Solution B was added dropwise to solution A, and a uniform solution was obtained after ultrasonic treatment for 10 min. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, and a uniform polymer solution was formed. It was placed in a reaction kettle and reacted at 180 °C for 6 h. After the reaction was completed, the reaction solution was centrifuged, and the liquid was removed and washed with DMF and methanol three times, respectively. Vacuum drying at 60 °C was performed. A black-brown powder was obtained.

[0094] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 50 %.

[0095] The black-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 PI / 1-S1-Fe1@C were obtained.

[0096] Example 18

[0097] 1.212 g of 3,3',4,4'-benzophenonetetracarboxylic dianhydride (1 mol) and 0.822 g of o-phenylenediamine (2 mol) were dissolved in 30 mL of DMF, denoted as solution A. 0.616 g of anhydrous ferric chloride (1 mol) and 1.142 g of thioacetamide (4 mol) were dissolved in 30 mL of DMF, denoted as solution B. Solution B was added dropwise to solution A, and a uniform solution was obtained after ultrasonic treatment for 10 min. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, and a uniform polymer solution was formed. It was placed in a reaction kettle and reacted at 180 °C for 6 h. After the reaction was completed, the reaction solution was centrifuged, and the liquid was removed and washed with DMF and methanol three times, respectively. Vacuum drying at 60 °C was performed. A black-brown powder was obtained.

[0098] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 50 %.

[0099] The black-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 PI / 2-S1-Fe1@C were obtained.

[0100] Example 19

[0101] 1.212 g of 3,3',4,4'-benzophenone dicarboxylic dianhydride (1 mol) and 0.822 g of m-phenylenediamine (2 mol) were dissolved in 30 mL of DMF, denoted as solution A. 0.616 g of anhydrous ferric chloride (1 mol) and 1.142 g of thioacetamide (4 mol) were dissolved in 30 mL of DMF, denoted as solution B. Solution B was added dropwise to solution A, and a uniform solution was obtained after ultrasonic treatment for 10 min. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, and a uniform polymer solution was formed. The reaction was carried out in a reaction kettle at 180 °C for 6 h. After the reaction was completed, the reaction solution was centrifuged, and the liquid was removed and washed with DMF and methanol three times, respectively. Vacuum drying was carried out at 60 °C. A black-brown powder was obtained.

[0102] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 50 %.

[0103] The black-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 PI / 3-S1-Fe1@C were obtained.

[0104] Example 20

[0105] 1.212 g of 3,3',4,4'-benzophenone dicarboxylic dianhydride (1 mol) and 0.822 g of p-phenylenediamine (2 mol) were dissolved in 30 mL of acetone, denoted as solution A. 0.616 g of anhydrous ferric chloride (1 mol) and 1.142 g of thioacetamide (4 mol) were dissolved in 30 mL of acetone, denoted as solution B. Solution B was added dropwise to solution A, and a uniform solution was obtained after ultrasonic treatment for 10 min. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, and a uniform polymer solution was formed. The reaction was carried out in a reaction kettle at 180 °C for 6 h. After the reaction was completed, the reaction solution was centrifuged, and the liquid was removed and washed with DMF and methanol three times, respectively. Vacuum drying was carried out at 60 °C. A black-brown powder was obtained.

[0106] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 50 %.

[0107] The black-brown powder obtained above was placed in a crucible and calcined at 500 °C for 3 h with a temperature rising rate of 5 °C / min, and finally sulfur-modified Fe-polymer-based self-assembled nanospheres (PI-S1-Fe1) 1@C were obtained.

[0108] Example 21

[0109] 1.212 g of 3,3',4,4'-benzophenone dicarboxylic dianhydride (1 mol) and 0.822 g of p-phenylenediamine (2 mol) were dissolved in 30 mL of N-methylpyrrolidone, and 0.616 g of anhydrous ferric chloride (1 mol) and 1.142 g of thioacetamide (4 mol) were dissolved in 30 mL of N-methylpyrrolidone, denoted as solution B. Solution B was added dropwise to solution A, and a uniform solution was obtained after ultrasonic treatment for 10 min. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, and a uniform polymer solution was formed. It was placed in a reaction kettle and reacted at 180 °C for 6 h. After the reaction was completed, the reaction solution was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times, respectively. Vacuum drying at 60 °C was performed. A black-brown powder was obtained.

[0110] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 50 %.

[0111] The black-brown powder obtained above was placed in a crucible and calcined at 500 °C for 3 h with a temperature rising rate of 5 °C / min, and finally sulfur-modified Fe-polymer-based self-assembled nanospheres (PI-S1-Fe1) 2@C were obtained.

[0112] Comparative Example 1

[0113] 1.212 g of 3,3',4,4'-benzophenone dicarboxylic dianhydride (1 mol) and 0.822 g of p-phenylenediamine (2 mol) were dissolved in 30 mL of N-methylpyrrolidone, and 0.616 g of anhydrous ferric chloride (1 mol) and 1.142 g of thioacetamide (4 mol) were dissolved in 30 mL of N-methylpyrrolidone, denoted as solution B. Solution B was added dropwise to solution A, and a uniform solution was obtained after ultrasonic treatment for 10 min. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, and a uniform polymer solution was formed. It was placed in a reaction kettle and reacted at 180 °C for 6 h. After the reaction was completed, the reaction solution was centrifuged, and the liquid was removed and washed with DMF and methanol for 3 times, respectively. Vacuum drying at 60 °C was performed. A black-brown powder was obtained.

[0114] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 50 %.

[0115] The black-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 obtain sulfur-modified Fe-polymer-based self-assembled nanosheets, denoted as 1 (PI-S1-Fe1)@C.

[0116] Comparative Example 2

[0117] 1.212 g of 3,3',4,4'-benzophenone dicarboxylic dianhydride (1 mol) and 3.659 g of p-phenylenediamine (9 mol) were dissolved in 30 mL of DMF, denoted as solution A. 0.616 g of anhydrous ferric chloride (1 mol) and 1.142 g of thioacetamide (4 mol) were dissolved in 30 mL of DMF, denoted as solution B. Solution B was added dropwise to solution A, and a uniform solution was obtained after ultrasonic treatment for 10 min. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, and a uniform polymer solution was formed. The reaction was carried out in a reaction kettle at 180 °C for 6 h. After the reaction was completed, the reaction solution was centrifuged, and the liquid was removed and washed with DMF and methanol three times, respectively. Vacuum drying was carried out at 60 °C. A black-brown powder was obtained.

[0118] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 50%.

[0119] The black-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 obtain sulfur-modified Fe-polymer-based self-assembled nanosheets, denoted as 2 (PI-S1-Fe1)@C.

[0120] Comparative Example 3

[0121] 1.212 g of 3,3',4,4'-benzophenone dicarboxylic dianhydride (1 mol) and 4.066 g of p-phenylenediamine (10 mol) were dissolved in 30 mL of DMF, denoted as solution A. 0.616 g of anhydrous ferric chloride (1 mol) and 1.142 g of thioacetamide (4 mol) were dissolved in 30 mL of DMF, denoted as solution B. Solution B was added dropwise to solution A, and a uniform solution was obtained after ultrasonic treatment for 10 min. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, and a uniform polymer solution was formed. The reaction was carried out in a reaction kettle at 180 °C for 6 h. After the reaction was completed, the reaction solution was centrifuged, and the liquid was removed and washed with DMF and methanol three times, respectively. Vacuum drying was carried out at 60 °C. A black-brown powder was obtained.

[0122] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 50%.

[0123] The black-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 obtain sulfur-modified Fe-polymer-based self-assembled nanosheets, denoted as 3(PI-S1-Fe1)@C.

[0124] Comparative Example 4

[0125] 1.212 g of 3,3',4,4'-benzophenone dicarboxylic dianhydride (1 mol) and 0.822 g of p-phenylenediamine (2 mol) were dissolved in 30 mL of DMF, denoted as solution A. 0.616 g of anhydrous ferric chloride (1 mol) and 0.565 g of thioacetamide (2 mol) were dissolved in 30 mL of DMF, denoted as solution B. Solution B was added dropwise to solution A, and a uniform solution was obtained after ultrasonic treatment for 10 min. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, and a uniform polymer solution was formed. The reaction was carried out in a reaction kettle at 180 °C for 6 h. After the reaction was completed, the reaction solution was centrifuged, and the liquid was removed and washed with DMF and methanol three times, respectively. Vacuum drying was carried out at 60 °C. A black-brown powder was obtained.

[0126] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 50%.

[0127] The black-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 obtain sulfur-modified Fe-polymer-based self-assembled nanosheets, denoted as 4(PI-S1-Fe1)@C.

[0128] Comparative Example 5

[0129] 1.212 g of 3,3',4,4'-benzophenone dicarboxylic dianhydride (1 mol) and 0.822 g of p-phenylenediamine (2 mol) were dissolved in 30 mL of DMF, denoted as solution A. 0.616 g of anhydrous ferric chloride (1 mol) and 0.848 g of thioacetamide (3 mol) were dissolved in 30 mL of DMF, denoted as solution B. Solution B was added dropwise to solution A, and a uniform solution was obtained after ultrasonic treatment for 10 min. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, and a uniform polymer solution was formed. The reaction was carried out in a reaction kettle at 180 °C for 6 h. After the reaction was completed, the reaction solution was centrifuged, and the liquid was removed and washed with DMF and methanol three times, respectively. Vacuum drying was carried out at 60 °C. A black-brown powder was obtained.

[0130] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 50%.

[0131] The black-brown powder obtained above was placed in a crucible and calcined at 500 °C for 3 h with a temperature increase rate of 5 °C / min to obtain sulfur-modified Fe-polymer-based self-assembled nanosheets, denoted as 5 (PI-S1-Fe1)@C.

[0132] Comparative Example 6

[0133] 1.212 g of 3,3',4,4'-benzophenone dicarboxylic dianhydride (1 mol) and 0.822 g of p-phenylenediamine (2 mol) were dissolved in 30 mL of DMF, denoted as solution A. 0.616 g of anhydrous ferric chloride (1 mol) and 2.825 g of thioacetamide (10 mol) were dissolved in 30 mL of DMF, denoted as solution B. Solution B was added dropwise to solution A, and a uniform solution was obtained after ultrasonic treatment for 10 min. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, and a uniform polymer solution was formed. The solution was placed in a reaction kettle and reacted at 180 °C for 6 h. After the reaction was completed, the reaction solution was centrifuged, and the liquid was removed and washed with DMF and methanol three times, respectively. Vacuum drying was performed at 60 °C. A black-brown powder was obtained.

[0134] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 50%.

[0135] The black-brown powder obtained above was placed in a crucible and calcined at 500 °C for 3 h with a temperature increase rate of 5 °C / min to obtain sulfur-modified Fe-polymer-based self-assembled nanosheets, denoted as 6 (PI-S1-Fe1)@C.

[0136] Comparative Example 7

[0137] 1.212 g of 3,3',4,4'-benzophenone dicarboxylic dianhydride (1 mol) and 0.822 g of p-phenylenediamine (2 mol) were dissolved in 30 mL of DMF, denoted as solution A. 0.616 g of anhydrous ferric chloride (1 mol) and 3.108 g of thioacetamide (11 mol) were dissolved in 30 mL of DMF, denoted as solution B. Solution B was added dropwise to solution A, and a uniform solution was obtained after ultrasonic treatment for 10 min. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, and a uniform polymer solution was formed. The solution was placed in a reaction kettle and reacted at 180 °C for 6 h. After the reaction was completed, the reaction solution was centrifuged, and the liquid was removed and washed with DMF and methanol three times, respectively. Vacuum drying was performed at 60 °C. A black-brown powder was obtained.

[0138] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 50%.

[0139] The black-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 obtain sulfur-modified Fe-polymer-based self-assembled nanosheets, denoted as 7 (PI-S1-Fe1)@C.

[0140] Comparative Example 8

[0141] 1.212 g of 3,3',4,4'-benzophenone dicarboxylic dianhydride (1 mol) and 0.822 g of p-phenylenediamine (2 mol) were dissolved in 30 mL of DMF, denoted as solution A. 0.616 g of anhydrous ferric chloride (1 mol) and 1.142 g of thioacetamide (4 mol) were dissolved in 30 mL of DMF, denoted as solution B. Solution B was added dropwise to solution A, and a uniform solution was obtained after ultrasonic treatment for 10 min. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, and a uniform polymer solution was formed. The reaction was carried out in a reaction kettle at 180 °C for 6 h. After the reaction was completed, the reaction solution was centrifuged, and the liquid was removed and washed with DMF and methanol three times, respectively. Vacuum drying was carried out at 60 °C. A black-brown powder was obtained.

[0142] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 5%.

[0143] The black-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 obtain sulfur-modified Fe-polymer-based self-assembled nanosheets, denoted as 7 (PI-S1-Fe1)@C.

[0144] Comparative Example 9

[0145] 1.212 g of 3,3',4,4'-benzophenone dicarboxylic dianhydride (1 mol) and 0.822 g of p-phenylenediamine (2 mol) were dissolved in 30 mL of DMF, denoted as solution A. 0.616 g of anhydrous ferric chloride (1 mol) and 1.142 g of thioacetamide (4 mol) were dissolved in 30 mL of DMF, denoted as solution B. Solution B was added dropwise to solution A, and a uniform solution was obtained after ultrasonic treatment for 10 min. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, and a uniform polymer solution was formed. The reaction was carried out in a reaction kettle at 180 °C for 6 h. After the reaction was completed, the reaction solution was centrifuged, and the liquid was removed and washed with DMF and methanol three times, respectively. Vacuum drying was carried out at 60 °C. A black-brown powder was obtained.

[0146] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 70%.

[0147] The black-brown powder obtained above was placed in a crucible and calcined at 500 °C for 3 h with a temperature rising rate of 5 °C / min, to obtain sulfur-modified Fe-polymer-based self-assembled nanosheets, denoted as 2(1PI-S1-Fe1)@C.

[0148] Comparative Example 10

[0149] 1.212 g of 3,3',4,4'-benzophenone dicarboxylic dianhydride (1 mol) and 0.822 g of p-phenylenediamine (2 mol) were dissolved in 30 mL of DMF, denoted as solution A. 0.616 g of anhydrous ferric chloride (1 mol) and 1.142 g of thioacetamide (4 mol) were dissolved in 30 mL of DMF, denoted as solution B. Solution B was added dropwise to solution A, and a uniform solution was obtained after ultrasonic treatment for 10 min. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, to form a uniform polymer solution. The solution was placed in a reaction kettle and reacted at 180 °C for 6 h. After the reaction was completed, the reaction solution was centrifuged, and the liquid was removed and washed three times with DMF and methanol, respectively. Vacuum drying was performed at 60 °C. A black-brown powder was obtained.

[0150] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 80%.

[0151] The black-brown powder obtained above was placed in a crucible and calcined at 500 °C for 3 h with a temperature rising rate of 5 °C / min, to obtain sulfur-modified Fe-polymer-based self-assembled nanosheets, denoted as 2(1PI-S1-Fe1)@C.

[0152] Comparative Example 11

[0153] 1.212 g of 3,3',4,4'-benzophenone dicarboxylic dianhydride (1 mol) and 0.822 g of p-phenylenediamine (2 mol) were dissolved in 30 mL of DMF, denoted as solution A. 0.616 g of anhydrous ferric chloride (1 mol) and 1.142 g of thioacetamide (4 mol) were dissolved in 30 mL of DMF, denoted as solution B. Solution B was added dropwise to solution A, and a uniform solution was obtained after ultrasonic treatment for 10 min. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, to form a uniform polymer solution. The solution was placed in a reaction kettle and reacted at 140 °C for 6 h. After the reaction was completed, the reaction solution was centrifuged, and the liquid was removed and washed three times with DMF and methanol, respectively. Vacuum drying was performed at 60 °C. A black-brown powder was obtained.

[0154] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 50%.

[0155] The black-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 obtain sulfur-modified Fe-polymer-based self-assembled nanosheets, denoted as PI-S1-Fe1@C.

[0156] Comparative Example 12

[0157] 1.212 g of 3,3',4,4'-benzophenone dicarboxylic dianhydride (1 mol) and 0.822 g of p-phenylenediamine (2 mol) were dissolved in 30 mL of DMF, denoted as solution A. 0.616 g of anhydrous ferric chloride (1 mol) and 1.142 g of thioacetamide (4 mol) were dissolved in 30 mL of DMF, denoted as solution B. Solution B was added dropwise to solution A, and a uniform solution was obtained after ultrasonic treatment for 10 min. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, and a uniform polymer solution was formed. The reaction was carried out in a reaction kettle at 180 °C for 4 h. After the reaction was completed, the reaction solution was centrifuged, and the liquid was removed and washed with DMF and methanol three times, respectively. Vacuum drying was carried out at 60 °C. A black-brown powder was obtained.

[0158] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 50%.

[0159] The black-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 obtain sulfur-modified Fe-polymer-based self-assembled nanosheets, denoted as PI-S1-Fe1@C. 4 h

[0160] Comparative Example 13

[0161] 1.212 g of 3,3',4,4'-benzophenone dicarboxylic dianhydride (1 mol) and 0.822 g of p-phenylenediamine (2 mol) were dissolved in 30 mL of DMF, denoted as solution A. 0.616 g of anhydrous ferric chloride (1 mol) and 1.142 g of thioacetamide (4 mol) were dissolved in 30 mL of DMF, denoted as solution B. Solution B was added dropwise to solution A, and a uniform solution was obtained after ultrasonic treatment for 10 min. The solution was stirred at room temperature at a stirring speed of 500 r / min until the reaction was complete, and a uniform polymer solution was formed. The reaction was carried out in a reaction kettle at 180 °C for 12 h. After the reaction was completed, the reaction solution was centrifuged, and the liquid was removed and washed with DMF and methanol three times, respectively. Vacuum drying was carried out at 60 °C. A black-brown powder was obtained.

[0162] The black-brown powder obtained above was etched using sulfuric acid with a concentration of 50%.

[0163] ​The black-brown powder obtained above was placed in a crucible and calcined at 500 °C for 3 h at a heating rate of 5 °C / min to obtain a sulfur-modified Fe-polymer-based self-assembled nanosheet, denoted as PI 12 h -S1-Fe1@C.

[0164] The catalysts prepared in combination with Examples 1-21 and Comparative Examples 1-13 were tested for their catalytic performance in the degradation of dyes by the photo-Fenton process, and the catalytic performance of the catalysts and the degradation ability of the catalysts for organic pollutants in wastewater were analyzed by calculating the decolorization rate of the dyes, as shown in Table 1.

[0165] The specific steps of the experiment are as follows: first, 100 mL of 4BS dye solution with a concentration of 50 mg / L was prepared, then 0.05-1.0 g of catalyst was weighed and added to the dye solution, and the solution was placed on a shaker. Before the photocatalytic degradation experiment, the reaction solution was stirred without light for 30 min to achieve adsorption equilibrium of the catalyst; hydrogen peroxide was added under light, and the degradation experiment was started under light, and the degradation time was 150 min. The sample was taken at regular intervals, filtered and tested for absorbance.

[0166] First, 100 mL of para-methylamphetamine with a concentration of 10 ng / L was prepared, then 0.05-1.0 g of catalyst was weighed and added to the solution, and the solution was placed on a shaker for 30 min of adsorption. The sample was taken at regular intervals, filtered and tested for absorbance. (Experimental test of Example 5)

[0167] First, 100 mL of ketamine with a concentration of 100 ng / L was prepared, then 0.05-1.0 g of catalyst was weighed and added to the solution, and the solution was placed on a shaker for 30 min of adsorption. The sample was taken at regular intervals, filtered and tested for absorbance. (Experimental test of Example 6)

[0168] There is a positive correlation between absorbance, concentration and optical path, and the Lambert-Beer law can be expressed by formula (1-1)

[0169]

[0170] In the above formula, A Absorbance; usually represented by A t A represents the absorbance of each sample, t is a natural number, and represents the sample order number;

[0171] ε Molar absorptivity;

[0172] b Liquid layer thickness, cm;

[0173] c - concentration of light-absorbing substance, mol-L -1 Generally, C t represents the concentration of light-absorbing substance measured at each sampling, t is a natural number, and indicates the sampling order number;

[0174] The pollution rate of macromolecular contaminant is calculated according to formula (1-2):

[0175]

[0176] In the above formula, η - pollution rate;

[0177] C - concentration of contaminant at a certain time of reaction, mg-L -1

[0178] C 0 - concentration of contaminant at initial time, mg-L -1

[0179] Taking Example 1 as an example, in formula (1-1), ε and b are fixed values, which can be offset in calculation, so that A absorbance is approximately equal to the concentration of C light-absorbing substance.

[0180] A absorbance is measured by ultraviolet spectrophotometer, A0≈C0=1.251

[0181] A t ≈C t (t represents the order number of each sampling) = 0.200

[0182] Therefore, the degradation ability of the catalyst to the organic contaminant in the wastewater is calculated by the decolorization rate: decolorization rate = 1-C t / C0=1-0.200 / 1.251 100%=84%

[0183] Table I:

[0184]

[0185] ​​

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 an acid anhydride, a phenylenediamine, an iron salt, and a thioacetamide in a mass ratio of 1:2-8:1:4-9, and the preparation method is as follows: (1) the acid anhydride and the phenylenediamine are dissolved in an organic solvent A to obtain solution A, the iron salt and the thioacetamide are dissolved in an organic solvent B to obtain solution B, the solution B is added dropwise into the solution A, and then the mixture is mixed by ultrasonic waves 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; the organic solvent A is DMF, and the organic solvent B is DMF; (2) the mixed solution is reacted at a temperature of 160-200 ℃ for 6-10 hours to obtain a reaction liquid; (3) the reaction liquid in step (2) is centrifuged, the liquid is removed, and then the obtained black-brown powder is washed with DMF and methanol respectively, and dried to obtain a black-brown powder; (4) the black-brown powder prepared in step (3) is etched with a sulfuric acid aqueous solution with a mass concentration of 10%-60% to obtain an etched black-brown powder; (5) the etched black-brown powder in step (4) is placed in a crucible and calcined at a temperature of 400-600 ℃ for 2-4 hours to obtain the sulfur-modified Fe-polymer-based self-assembled nanospheres, and the calcination temperature increasing rate is 2-5 ℃ / min.

2. The sulfur-modified Fe-polymer-based self-assembled nanospheres of claim 1, wherein, The acid anhydride is one or more of pyromellitic dianhydride and 3,3',4,4'-benzophenonetetracarboxylic dianhydride.

3. The sulfur-modified Fe-polymer-based self-assembled nanospheres of claim 1, wherein The phenylenediamine is one or more of p-phenylenediamine, o-phenylenediamine, and m-phenylenediamine.

4. The sulfur-modified Fe-polymer-based self-assembled nanospheres of claim 1, wherein, The iron salt is an organic iron salt or an inorganic iron salt, the organic iron salt is acetylacetone iron, 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 as described in any one of claims 2-4, characterized in that, The mass ratio of the acid anhydride, the phenylenediamine, the iron salt, and the thioacetamide is 1:2:1:

4.

6. The sulfur-modified Fe-polymer-based self-assembled nanospheres of claim 1, wherein, The reaction in step (2) is performed at a temperature of 180 ℃ for 6 hours to obtain a reaction liquid.

7. The sulfur-modified Fe-polymer-based self-assembled nanospheres of claim 1, wherein, The drying in step (3) is performed at 60 ℃ for 12 hours under vacuum.

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

9. The sulfur-modified Fe-polymer-based self-assembled nanospheres according to claim 1 are used as a degradation catalyst for degrading organic pollutants in wastewater.

10. Use according to claim 9, wherein The application method is as follows: 0.05-1.0 % of the sulfur-modified Fe-polymer-based self-assembled nanospheres are added into wastewater containing organic pollutants as a catalyst, the wastewater is shaken for 30-60 min, and then hydrogen peroxide is added under light to continue the reaction.

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