CN111804322A - Preparation method and application of persulfate-activated nitrogen-doped graphene loaded carbon nitride composite material - Google Patents
Preparation method and application of persulfate-activated nitrogen-doped graphene loaded carbon nitride composite material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 68
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 57
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/305—Endocrine disruptive agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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Abstract
The invention provides a nitrogen-doped graphene loaded carbon nitride composite material for activating persulfateThe preparation method of the material and the application thereof comprises the following steps: s1, selecting commercial graphene, melamine and urea as raw materials; s2, mixing, namely uniformly mixing the commercial graphene, the melamine and the urea; s3, calcining, namely placing the commercial graphene, melamine and urea which are uniformly mixed in the step S2 in a tube furnace under the nitrogen atmosphere, calcining at the temperature of 500-600 ℃, controlling the heating rate at 3-8 ℃/min, keeping the temperature at 220-250min, and cooling to room temperature under the nitrogen atmosphere to obtain the nitrogen-doped graphene loaded carbon nitride composite material g-C for activating persulfate3N4/rGO-N, the g-C3N4the/rGO-N has high-efficiency effect on removing novel pollutants such as endocrine disruptors BPA, antibiotics CIP and the like and conventional dyes AO7 and OG, and the novel oxidation system has less catalyst and oxidant dosage and lower cost.
Description
Technical Field
The invention relates to a preparation method of a nitrogen-doped graphene loaded carbon nitride composite material and an application of the nitrogen-doped graphene loaded carbon nitride composite material in a persulfate-based advanced oxidation water treatment technology, and belongs to the technical field of water pollution control.
Background
Advanced oxidation technologies such as fenton, fenton-like, and photocatalytic technologies have been an effective method for degrading organic pollutants over the last several decades. Compared to these AOPs based on hydroxyl radicals (. OH), the activated Persulfate (PS) technology has been developed in recent years as a sulfate radical (SO)4 ·-) Novel AOPs that degrade contaminants for the main active species. It has a higher redox potential, it enables the rapid decomposition of most organic pollutants that are difficult to biodegrade, and the ultimate mineralization of CO2、H2O and inorganic salts, and therefore, the activated persulfate technology has become a focus of research in the field of pollution control in recent years. However, at room temperature, PS is very stable and thus has low activity, and O-O bonds should be cleaved to generate highly active species (e.g., SO)4 ·-OH or1O2Etc.) require energy or chemical activators to the persulfate anion. Common energy sources mainly comprise ultraviolet light, heating, wave radiation, ultrasound, ionizing radiation and the like, and chemical activators mainly comprise transition metal ions, metal oxides, alkali and the like, but the activation modes have the defects of metal ion flow, high energy consumption and the like. Therefore, the development of new metal loss rate is low or even no metal loss is causedAnd catalysts that do not consume other energy sources are the focus of current research.
In recent years, metal-free catalysts have received much attention. Carbon nanomaterials, such as Carbon Nanotubes (CNTs), graphene, have the characteristics of surface chemical inertness, good electrical conductivity, large specific surface area and pore volume, and the like, and have been shown to have a better catalytic effect in various degradation processes. The introduction of carbon nanomaterials into environmental catalysis, as a metal-free heterogeneous catalyst, for the removal of organic contaminants from water would be very promising. Doping carbon nanomaterials with heteroatoms such as nitrogen, sulfur, phosphorus, boron and the like is an effective means for enhancing the catalytic activity of the carbon nanomaterials, and has become a hot spot of research in recent years.
In recent years, a new type of visible light responsive semiconductor photocatalyst graphite phase carbon nitride (g-C)3N4) Arouse more and more attention of scholars. g-C in comparison with other semiconductor catalysts3N4The preparation method is nontoxic and cheap, can be directly synthesized by thermal shrinkage of nitrogen-rich precursors such as melamine, dicyandiamide and the like, and is easy to obtain. However, the method takes a long time to treat the organic wastewater independently, needs to consume other additional energy sources, and has no ideal effect on the degradation of the organic matters. To solve this problem, researchers have mixed g-C with other oxidants3N4The combination enhances the degradation efficiency of the organic matters. For example, there is a large amount of g-C3N4Reports of synergistic persulfate degradation of pollutants under visible light, but most of the reports are g-C3N4As a research of the photocatalyst, when the photocatalyst is coupled with persulfate, an additional light source is also needed. There have also been some studies of persulfate activators, but these catalysts are mostly metals with g-C3N4Of a non-metallic g-C3N4Composite materials are less studied.
In view of g-C3N4With higher N content and rich graphite nitrogen, we tried to get g-C3N4Loaded on a graphene material to prepare a non-metal catalyst capable of efficiently catalytically decomposing PMS degradation pollutants under the condition of no illumination. The research result can provide a new idea and reference for the application of the simple and cheap carbon nitride-loaded catalyst in catalyzing persulfate to degrade pollutants in environmental remediation.
Disclosure of Invention
Technical problem to be solved
The problem to be solved by the invention is to mix g-C3N4The non-metal catalyst which can efficiently catalyze and decompose PMS degradation pollutants under the condition of no illumination is prepared by being loaded on a graphene material, and the rGO, melamine and urea are synchronously pyrolyzed and thermally condensed by adopting a one-step method to obtain a novel PMS catalyst g-C3N4/rGO-N。
(II) technical scheme
One purpose of the invention is to provide a preparation method of a nitrogen-doped graphene loaded carbon nitride composite material for activating persulfate, which comprises the following steps:
s1, selecting commercial graphene, melamine and urea as raw materials;
s2, mixing, namely uniformly mixing the commercial graphene, the melamine and the urea;
and S3, calcining, namely placing the commercial graphene, melamine and urea which are uniformly mixed in the step S2 in a tube furnace under the nitrogen atmosphere, calcining at the temperature of 500-600 ℃, keeping the temperature rise rate at 3-8 ℃/min, keeping the temperature at 220-250min, and cooling to room temperature under the nitrogen atmosphere to obtain the nitrogen-doped graphene loaded carbon nitride composite material for activating persulfate.
In one aspect, the mass ratio of the commercial graphene, melamine and urea in step S1 is (1: 1: 1)
In one aspect, the commercial graphene is prepared for a reduction oxidation process with SSA >400m 2/g.
In one aspect, the temperature in step S3 is controlled at 500 deg.C, 550 deg.C, 600 deg.C.
In one aspect, the temperature rise rate in step S3 is controlled at 5 deg.C/min, and the temperature is kept constant for 240 min.
Another object of the present invention is to provide a nitrogen-doped graphene-supported carbon nitride composite material for activating persulfate, and an application thereof in removing pollutants in water.
In one aspect, the persulfate-activated nitrogen-doped graphene-loaded carbon nitride composite material is applied to removal of one or more combined pollutants of endocrine disruptors BPA, antibiotics CIP, dyes AO7 and dyes OG in water.
The invention also aims to provide an application method of the nitrogen-doped graphene-loaded carbon nitride composite material for activating persulfate in removing pollutants in water, which comprises the following steps of taking a certain amount of the nitrogen-doped graphene-loaded carbon nitride composite material as a catalyst, adding the catalyst into sewage to be treated, adding PMS (polyethylene glycol styrene) serving as an oxidant, and stirring or oscillating or standing for 30min at normal temperature.
Wherein the sewage to be treated contains dye AO7 and/or dye OG, and the mass ratio of the nitrogen-doped graphene loaded carbon nitride composite material to PMS is 20: 307. and the sewage to be treated contains endocrine disruptors BPA and/or antibiotics CIP, and the mass ratio of the nitrogen-doped graphene loaded carbon nitride composite material to PMS is 30: 307.
(III) advantageous effects
Firstly, compared with other catalysts, the catalyst prepared by the preparation method of the nitrogen-doped graphene loaded carbon nitride composite material for activating persulfate provided by the invention is nontoxic and cheap, can be directly synthesized by thermally shrinking nitrogen-rich precursors such as melamine and dicyandiamide, and is easy to obtain;
secondly, the raw material for preparing the nitrogen-doped graphene-loaded carbon nitride composite material for activating persulfate provided by the invention adopts graphene, has the characteristics of surface chemical inertness, good conductivity, large specific surface area, pore volume and the like, and has a good catalytic effect in various degradation processes, so that the carbon nanomaterial is introduced into environment catalysis to be used as a metal-free heterogeneous catalyst, organic pollutants in water can be effectively removed, and meanwhile, the carbon nanomaterial is environment-friendly and has no secondary pollution such as metal leaching;
finally, the catalyst prepared by the preparation method of the nitrogen-doped graphene loaded carbon nitride composite material for activating persulfate provided by the invention has an efficient effect on removing novel pollutants such as endocrine disruptors BPA, antibiotics CIP and the like and conventional dyes AO7 and OG, and the novel oxidation system has less catalyst and oxidant addition amount and lower cost.
Drawings
Fig. 1 is an XRD diffraction spectrum of the prepared nitrogen-doped graphene-supported carbon nitride composite material.
Fig. 2 is a raman spectrum of the prepared nitrogen-doped graphene-supported carbon nitride composite material.
Fig. 3 is SEM and TEM images of the prepared nitrogen-doped graphene-supported carbon nitride composite material.
Fig. 4 is a BET diagram of the prepared nitrogen-doped graphene-supported carbon nitride composite material.
Fig. 5 is an XPS diagram of the prepared nitrogen-doped graphene-supported carbon nitride composite material.
Fig. 6 is a graph of the removal effect of the prepared nitrogen-doped graphene-loaded carbon nitride composite material on the dye AO 7.
Fig. 7 is a graph showing the effect of the prepared nitrogen-doped graphene loaded carbon nitride composite material on OG, CIP and BPA removal.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The preparation method of the nitrogen-doped graphene loaded carbon nitride composite material for activating persulfate comprises the following steps: s1, selecting commercial graphene, melamine and urea as raw materials; s2, mixing, namely uniformly mixing the commercial graphene, the melamine and the urea; s3, calcining, namely placing the commercial graphene, melamine and urea which are uniformly mixed in the step S2 in a tube furnace under the nitrogen atmosphere, calcining at the temperature of 500-600 ℃, controlling the heating rate at 3-8 ℃/min, keeping the temperature at 220-250min, and cooling to room temperature under the nitrogen atmosphere to obtain the nitrogen-doped graphene loaded carbon nitride composite material g-C for activating persulfate3N4/rGO-N. Wherein g-C3N4the/rGO-N is non-toxic,The preparation method is cheap, can be directly synthesized by thermally shrinking nitrogen-rich precursors such as melamine, dicyandiamide and the like, and is easy to obtain.
In step S1, the mass ratio of the commercial graphene, melamine, and urea is (1: 1: 1).
Whereas commercial graphene is prepared by a reduction-oxidation method, SSA>400m2(ii) in terms of/g. The temperature in the step S3 is controlled to 500 deg.C, 550 deg.C, 600 deg.C, preferably 550 deg.C. In the step S3, the temperature rising rate is controlled at 5 ℃/min, and the temperature is kept for 240 min.
Example 1
The preparation method of the nitrogen-doped graphene loaded carbon nitride composite material for activating persulfate comprises the following specific steps:
respectively mixing 5g rGO, 5g melamine and 5g urea, placing in 20ml corundum crucible with cover, sealing with aluminum foil, and placing into a sealed container filled with N2Calcining in a 30min tubular furnace at different temperatures respectively. The calcination time can be selected from any time point of 220 to 250min, preferably the calcination time is 220, 240, 250min, and most preferably 240 min. When the calcination time is less than 220min or more than 250min, g-C of the product can be prepared3N4Part of the graphite crystal structure in/rGO-N causes damage. The heating rate can be controlled at any rate of 3-8 deg.C/min, such as 3 deg.C/min, 5 deg.C/min, or 8 deg.C/min. When the temperature rise rate is lower than 3 ℃/min, the whole preparation time is long, and when the temperature rise rate is higher than 8 ℃/min, the temperature change speed inside and outside the graphite crystal is not uniform, so that the stability of the final structure of the product is influenced. The optimal temperature rise rate can be selected to be 5 ℃/min. Cooling to room temperature in nitrogen atmosphere to obtain the final product g-C3N4/rGO-N. And performing experimental analysis on the characterization of the nitrogen-doped graphene loaded carbon nitride product.
Wherein the prepared material morphology structure is observed with JEM-2100F Transmission Electron Microscope (TEM) (JEOL, Japan) and Quanta400FEG Scanning Electron Microscope (SEM) (FEI, USA); the crystal structure was characterized on an XR-7000 type diffractometer (XRD) from Shimadzu, Japan. The surface elemental composition was analyzed using the ESCALAB250XIX ray photoelectron spectroscopy (XPS) system (ThermoFisherScientific, USA). The BET test utilizes a TriStarII3020 specific surface area and porosity analyzer. Raman spectra were collected using a raman microscope (labrammr. volume, HORIBAJY, France).
Fig. 1 is a result of a characteristic analysis of the crystal image structure on an XR-7000 type diffractometer (XRD) of shimadzu, japan, and a characteristic peak of 26 ° was seen in all samples, and no significant shift of these diffraction peaks was found, which means that the doping process did not significantly destroy the graphite crystal structure. FIG. 2 is a Raman spectrum of the nitrogen-doped graphene-loaded carbon nitride composite material, from which g-C is known3N4the/rGO-N has a relatively low intensity ratio (ID/IG) and a high quality. The wrinkling and stacked layer morphology of the two graphene samples can be observed in the SEM micrograph of fig. 3. The wrinkled sheet morphology was further revealed by TEM. As shown in the BET diagram of FIG. 4, g-C3N4Type IV isotherms of/rGO-N indicate the presence of mesopores and have a large specific surface area. The XPS analysis of FIG. 5 shows that g-C3N4The nitrogen content of/rGO-N is 14 at.%, and mainly contains N-6 (pyridine N), N-5 (pyrrole N) and (N-Q) graphite N and (N-A) amino N.
Example 2
The test for removing the dye AO7 by using the persulfate-activated nitrogen-doped graphene loaded carbon nitride composite material is as follows:
the persulfate-activated nitrogen-doped graphene-loaded carbon nitride composite material prepared in example 1 was selected as a raw material and subjected to a comparative test.
Wherein 20mg/Lg-C is added into 50mg/LAO7 solution3N4(rGO-N) and 307mg/LPMS, at intervals, samples were taken and g-C was removed by filtration3N4Adding methanol to terminate the reaction, and analyzing the change of the concentration of AO7 in the reaction solution by using an ultraviolet spectrophotometer.
For comparison, conventional rGO and its N-doped samples or classical metal catalysts (Co) were added separately3O4And Fe3O4) As the catalyst, the other conditions were the same as above.
Or g-C alone3N4The other conditions are the same as above without PMS.
The PMS is added into the reactor separately,without addition of g-C3N4and/rGO-N, other conditions are the same as above.
As shown in FIG. 6A, conventional rGO and its N-doped samples or classical metal catalysts (Co) with lower catalyst and oxidant usage3O4And Fe3O4) The PMS was not effectively activated to remove AO 7. As can be seen from fig. 6B, simple heat treatment of rGO did not enhance its activity. In addition, when only the oxidant PMS itself or the activator alone g-C is added3N4when/rGO-N is added into the system, the removal rate of AO7 is less than 10% in 30 minutes, which shows the direct oxidation and g-C of PMS3N4The adsorption route of/rGO-N on AO7 is negligible. However, when g-C is added simultaneously3N4at/rGO-N and PMS, AO7 was almost completely removed at 30 min.
Example-
The removal test for removing the dye OG from the persulfate-activated nitrogen-doped graphene loaded carbon nitride composite material through PMS activation specifically comprises the following steps:
adding 20mg/Lg-C into 100mg/L OG solution3N4(rGO-N) and 307mg/LPMS, at intervals, samples were taken and g-C was removed by filtration3N4and/rGO-N, analyzing OG concentration change in the reaction solution by adopting a spectrophotometer. As shown in FIG. 7, 100% of OG can be removed after 30 min.
Example 4
The removal test for removing the antibiotic CIP by activating PMS of the persulfate-activated nitrogen-doped graphene-loaded carbon nitride composite material is as follows:
adding 30mg/Lg-C into 20mg/LCIP solution3N4(rGO-N) and 307mg/LPMS, at intervals, samples were taken and g-C was removed by filtration3N4and/rGO-N, analyzing the change of the CIP concentration in the reaction solution by adopting liquid chromatography. As shown in fig. 7, CIP was almost completely removed after 30 min.
Example 5
The test for removing endocrine disruptors BPA by activating PMS with the persulfate-activated nitrogen-doped graphene-loaded carbon nitride composite material is as follows:
in 20mg/LBPA solutionAdding 30mg/Lg-C3N4(rGO-N) and 307mg/LPMS, at intervals, samples were taken and g-C was removed by filtration3N4and/rGO-N, analyzing the change of the concentration of the BPA in the reaction solution by adopting liquid chromatography. As shown in FIG. 7, BPA was 100% removed after 30 min.
Simultaneously mixing two or more of 20mg/LBPA, 20mg/LCIP, 20mg/LAO7 and 20mg/LOG solutions respectively, and adding a certain amount of g-C3N4Pergo-N and PMS, at intervals, samples were taken and g-C was removed by filtration3N4and/rGO-N, analyzing the concentration change of the mixed liquid residual substances in the reaction solution by adopting liquid chromatography, and removing the mixed liquid residual substances by 100 percent after 30 min.
It can be seen that catalysts g-C prepared according to the invention3N4the/rGO-N has high-efficiency effect on removing novel pollutants such as endocrine disruptors BPA, antibiotics CIP and the like and conventional dyes AO7 and OG, and the novel oxidation system has less catalyst and oxidant dosage and lower cost.
In summary, the above embodiments are not intended to be limiting embodiments of the present invention, and modifications and equivalent variations made by those skilled in the art based on the spirit of the present invention are within the technical scope of the present invention.
Claims (10)
1. A preparation method of a nitrogen-doped graphene loaded carbon nitride composite material with persulfate activated is characterized by comprising the following steps:
s1, selecting commercial graphene, melamine and urea as raw materials;
s2, mixing, namely uniformly mixing the commercial graphene, the melamine and the urea;
and S3, calcining, namely placing the commercial graphene, melamine and urea which are uniformly mixed in the step S2 in a tube furnace under the nitrogen atmosphere, calcining at the temperature of 500-600 ℃, keeping the temperature rise rate at 3-8 ℃/min, keeping the temperature at 220-250min, and cooling to room temperature under the nitrogen atmosphere to obtain the nitrogen-doped graphene loaded carbon nitride composite material for activating persulfate.
2. The preparation method of the persulfate-activated nitrogen-doped graphene-supported carbon nitride composite material according to claim 1, wherein the mass ratio of the commercial graphene, the melamine and the urea in the step S1 is (1: 1: 1).
3. The method for preparing the persulfate-activated nitrogen-doped graphene-loaded carbon nitride composite material according to claim 2, wherein the commercial graphene is prepared by a reduction-oxidation method, SSA>400m2/g。
4. The preparation method of the persulfate-activated nitrogen-doped graphene-supported carbon nitride composite material according to claim 3, wherein the temperature in the S3 step is controlled at 500 ℃, 550 ℃ and 600 ℃.
5. The preparation method of the persulfate-activated nitrogen-doped graphene-loaded carbon nitride composite material according to claim 4, wherein in the step S3, the temperature rise rate is controlled at 5 ℃/min, and the temperature is kept constant for 240 min.
6. Use of persulfate-activated nitrogen-doped graphene-loaded carbon nitride composite material in removal of pollutants in water, characterized in that the nitrogen-doped graphene-loaded carbon nitride composite material is prepared by the method for preparing persulfate-activated nitrogen-doped graphene-loaded carbon nitride composite material according to any one of claims 1 to 5.
7. Use of persulfate-activated nitrogen-doped graphene-loaded carbon nitride composite material in removal of one or more combined pollutants of endocrine disruptors BPA, antibiotics CIP, dyes AO7 and dyes OG in water, characterized in that the nitrogen-doped graphene-loaded carbon nitride composite material is prepared by the persulfate-activated nitrogen-doped graphene-loaded carbon nitride composite material preparation method according to any one of claims 1 to 5.
8. The application method of the persulfate-activated nitrogen-doped graphene-loaded carbon nitride composite material in removing pollutants in water is characterized by comprising the following steps of taking a certain amount of the nitrogen-doped graphene-loaded carbon nitride composite material prepared by the persulfate-activated nitrogen-doped graphene-loaded carbon nitride composite material preparation method according to any one of claims 1 to 6 as a catalyst, adding the catalyst into the sewage to be treated, adding PMS (poly-ammonium-sulfonate) serving as an oxidant, and stirring or oscillating or standing at normal temperature.
9. The application method of the persulfate-activated nitrogen-doped graphene-loaded carbon nitride composite material in removing pollutants in water according to claim 8, wherein the sewage to be treated contains AO7 and/or OG, and the mass ratio of the nitrogen-doped graphene-loaded carbon nitride composite material to PMS is 20: 307.
10. the application method of the persulfate-activated nitrogen-doped graphene-loaded carbon nitride composite material in removing pollutants in water according to claim 8, wherein the sewage to be treated is a sewage containing endocrine disruptors BPA and/or antibiotics CIP, and the mass ratio of the nitrogen-doped graphene-loaded carbon nitride composite material to PMS is 30: 307.
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