CN114950428B - Preparation method of catalyst for removing endocrine disruptors, catalyst and application of catalyst - Google Patents

Preparation method of catalyst for removing endocrine disruptors, catalyst and application of catalyst Download PDF

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CN114950428B
CN114950428B CN202210372288.XA CN202210372288A CN114950428B CN 114950428 B CN114950428 B CN 114950428B CN 202210372288 A CN202210372288 A CN 202210372288A CN 114950428 B CN114950428 B CN 114950428B
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catalyst
based material
modified carbon
solution
bisphenol
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CN114950428A (en
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刘杨
张永丽
霍晓卫
程丰
周鹏
童永飞
杨波
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Sichuan University
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Sichuan University
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • 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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention provides a preparation method of a catalyst for removing endocrine disruptors, the catalyst and application thereof, wherein the method comprises the following steps: preparing a boron (B) modified carbon-based material by adopting a hydrothermal method; adding deionized water into the modified carbon-based material B to dissolve the modified carbon-based material B to form a first solution, and adding ferric sulfate heptahydrate into the solution while stirring after ultrasonic treatment for 10min to form a second solution; dropwise adding sodium borohydride solution into the second solution at a preset dropwise adding rate under a protective atmosphere to load nano zero-valent iron on the B modified carbon-based material, and stirring for a preset time to obtain a first crude product; the catalyst for removing endocrine disruptors is obtained by repeatedly washing the first crude product by using ethanol and deionized water as detergents and drying the first crude product for a preset time in a vacuum freeze dryer.

Description

Preparation method of catalyst for removing endocrine disruptors, catalyst and application of catalyst
Technical Field
The invention relates to the field of wastewater treatment, in particular to a preparation method of a catalyst for removing endocrine disruptors, the catalyst and application thereof.
Background
Endocrine disruptors, also known as environmental hormones, are chemical substances that exogenously interfere with the endocrine system, that is, substances that exist in the environment and interfere with various links of the endocrine system of humans or animals and cause abnormal effects, and they do not directly act as toxic substances on organisms through various ways such as ingestion and accumulation, but act like estrogens on organisms, and even if the number is very small, the endocrine of organisms is unbalanced, and various abnormal phenomena occur. Such substances can lead to actuation of the object and the genital disorder of the human body, abnormal behavior, reduced reproductive capacity, death of the larvae, and even extinction.
Zero-valent iron (ZVI) has proven to be a promising sewage remediation technology due to its high reducing power, environmental friendliness and cost effectiveness. Persulfate is activated with zero-valent iron, since it gradually releases Fe 2+ And the activation of persulfates to produce sulfate radicals over a long period of time has attracted considerable attention. The nanoscale zero-valent iron (nZVI) has small particles and high activity, and can improve the activity of persulfate for degrading pollutants. However, nZVI undergoes rapid aggregation in solution due to magnetic interactions, thereby reducing its effectiveness. To solve this problem, porous materials such as biochar, resin, natural zeolite, silica, and the like have been used as carriers for nZVI to improve dispersibility. The nano iron is loaded on the carbon material, and endocrine disruptors in the water environment can be removed with higher efficiency through adsorption, free radical oxidation and non-free radical oxidation.
In the prior art, porous materials such as biochar are commonly used for loading nano zero-valent iron to activate a persulfate system, but the activation capability of the porous materials to persulfate is not strong, the catalysis effect is limited, and the way of activating persulfate is single, so that the removal efficiency of endocrine disruptors is difficult to improve.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a catalyst for removing endocrine disruptors, the catalyst and application thereof. The specific contents are as follows:
in a first aspect, the present invention provides a method for preparing a catalyst for endocrine disruptor removal, the method comprising:
step 1, preparing a B modified carbon-based material by adopting a hydrothermal method;
step 2, adding deionized water into the modified carbon-based material B to dissolve the modified carbon-based material B to form a first solution, and adding ferric sulfate heptahydrate into the solution while stirring after ultrasonic treatment for 10min to form a second solution;
step 3, dropwise adding sodium borohydride solution into the second solution at a preset dropwise adding rate under a protective atmosphere to load nano zero-valent iron on the B modified carbon-based material, and stirring for a preset time to obtain a first crude product;
and 4, repeatedly washing the first crude product by using ethanol and deionized water as detergents, and drying in a vacuum freeze dryer for a preset time to obtain the catalyst for removing endocrine disruptors.
Preferably, the method for preparing the B-modified carbon-based material by using the hydrothermal method in the step 1 includes:
step 1-1, respectively weighing coffee grounds, boric acid and sodium bicarbonate, adding the coffee grounds, the boric acid and the sodium bicarbonate into deionized water, stirring the mixture at 80 ℃ for 6 hours, and then placing the mixture into an oven at 80 ℃ for drying for 12 hours;
step 1-2, placing the mixture dried in the step 1-1 into a tube furnace, heating to 800 ℃, calcining for 2 hours in nitrogen atmosphere, and naturally cooling to room temperature to obtain a second crude product;
and 1-3, grinding the second crude product, cleaning with ethanol and deionized water, and placing in a drying box at 80 ℃ for drying to obtain the B modified carbon-based material.
Preferably, the mass ratio of the B modified carbon-based material to the iron sulfate heptahydrate is 1:0.4-1.4.
Preferably, the concentration of the sodium borohydride solution is 10g/L; the volume ratio of the mixed solution to the sodium borohydride solution is 2:1.
Preferably, the protective atmosphere is nitrogen or inert gas atmosphere.
Preferably, the preset dripping rate is 2 drops/s, and the stirring preset time is 30 minutes.
Preferably, the mass ratio of the coffee grounds to the sodium bicarbonate to the boric acid is 5:7:0.7-2.8; the mass ratio of the coffee grounds to the deionized water is 1-5:60.
Preferably, the heating rate to 800 ℃ is 5 ℃/min.
In a second aspect, the present invention provides a catalyst for endocrine disruptor removal, the catalyst being obtained by the preparation method of any one of the first aspects, the catalyst comprising: and B modified carbon-based material and nano zero-valent iron loaded on the B modified carbon-based material.
In a third aspect, the present invention provides a method for removing endocrine disruptors, adding the catalyst of the second aspect to wastewater containing bisphenol endocrine disruptors, and simultaneously adding persulfate to remove bisphenol endocrine disruptors in the wastewater.
Preferably, the addition amount of the catalyst is 0.04-0.08g/L, the addition amount of the persulfate is 0.5-2.0mmol/L, and the initial pH value of the wastewater is 4.65-10.74.
Compared with the prior art, the invention has the following advantages:
the embodiment of the invention provides a preparation method of a catalyst for removing endocrine disruptors, which adopts a hydrothermal method to prepare a B modified carbon-based material; adding deionized water into the modified carbon-based material B to dissolve the modified carbon-based material B to form a first solution, and adding ferric sulfate heptahydrate into the solution while stirring after ultrasonic treatment for 10min to form a second solution; dropwise adding sodium borohydride solution into the second solution at a preset dropwise adding rate under a protective atmosphere to load nano zero-valent iron on the B modified carbon-based material, and stirring for a preset time to obtain a first crude product; and repeatedly washing the first crude product by using ethanol and deionized water as detergents, and drying in a vacuum freeze dryer for a preset time to obtain the catalyst for removing endocrine disruptors.
According to the embodiment of the invention, the carbon-based material is subjected to B modification doping and nano zero-valent iron is loaded to activate persulfate, so that the removal efficiency of bisphenol endocrine disruptors is improved. According to the embodiment of the invention, the B modified carbon-based material is applied to the removal of endocrine disruptors, so that the electron transfer between persulfate and bisphenol A can be accelerated, the removal efficiency of the endocrine disruptors is improved, meanwhile, as the B modified material is loaded with nano zero-valent iron, the composite material has an electron transfer path in the process of removing the endocrine disruptors, nano zero-valent iron can activate persulfate to obtain sulfate radicals, hydroxyl radicals and the like, a free radical oxidation path is provided, the removal efficiency of the endocrine disruptors is further improved under the synergistic effect of the two paths, and in addition, as the zero-valent iron and B have a certain synergistic effect, the B modified carbon-based material loaded with nano zero-valent iron can obtain a metastable structure in the process of removing the endocrine disruptors, the oxidation potential of the carbon-based material is improved, the electron transfer process is further accelerated, and the activation effect of the B modified carbon-based material loaded with nano zero-valent iron on the persulfate is further improved, so that the removal efficiency of the endocrine disruptors is improved. In the embodiment of the invention, the B modified carbon-based material loaded with nano zero-valent iron and persulfate are added, and the removal rate of bisphenol A in 60min can be close to 100%.
Drawings
FIG. 1 shows a flow chart of the steps of a method for preparing a B modified carbon-based material loaded with nano zero-valent iron in an embodiment of the invention;
FIG. 2 shows a surface topography of a catalyst for endocrine disruptor removal prepared in example 1 of the present invention; wherein, fig. 2 (a), (b) show electron micrographs of the catalyst for endocrine disruptor removal prepared in example 1 of the present invention, and fig. 2 (c) shows SEM images and (EDX) element maps of the catalyst for endocrine disruptor removal prepared in example 1 of the present invention;
FIG. 3 shows a TEM image of a catalyst for endocrine disruptor removal prepared in example 1 of the present invention;
FIG. 4 shows XPS spectra before and after the reaction of the catalyst for endocrine disruptor removal prepared in example 1 of the present invention;
FIG. 5 shows XPS spectra of the combined states of C1 s, O1 s, B1s and Fe2p before and after the reaction of the catalyst for endocrine disruptor removal prepared in example 1 of the present invention; wherein, the figures 5 (a) -5 (d) are XPS spectra of the combined states of C1 s, O1 s, B1s and Fe2p before the reaction respectively; FIG. 5 (e) -FIG. 5 (h) are XPS spectra of the combined states of C1 s, O1 s, B1s and Fe2p after the reaction, respectively;
FIG. 6 shows XRD patterns before and after the reaction of the catalyst for endocrine disruptor removal prepared in example 1 of the present invention;
FIG. 7 shows a model map of nZVI@BCs adsorption BPA; wherein fig. 7 (a) shows a pseudo-first order kinetic model diagram of the adsorption of BPA by nzvi@bcs, fig. 7 (b) shows a pseudo-second order kinetic model diagram of the adsorption of BPA by nzvi@bcs, and fig. 7 (c) shows a particle internal diffusion model diagram of the adsorption of BPA by nzvi@bcs.
FIG. 8 shows a graph of the adsorption of nZVI@BCs to BPA; wherein fig. 8 (a) shows an adsorption isotherm plot of nzvi@bcs adsorbing BPA, fig. 8 (b) shows a Langmuir fit plot of nzvi@bcs adsorbing BPA, and fig. 8 (c) shows a Freundlich fit plot of nzvi@bcs adsorbing BPA;
FIG. 9 shows a comparative graph of bisphenol A, total organic carbon removal effect of example 1, comparative example 1 and comparative example 2 of the present invention; wherein, fig. 9 (a) shows bisphenol a removal graphs of inventive example 1, comparative example 1 and comparative example 2, and fig. 9 (b) shows total organic carbon removal graphs of inventive example 1, comparative example 1 and comparative example 2; FIGS. 9 (c) and 9 (d) are graphs showing the reaction rates during bisphenol A removal of comparative example 2 and example 1 of the present invention, respectively;
FIG. 10 shows a 3D EEM fluorescence spectrum of bisphenol A during the reaction for the catalyst for endocrine disruptor removal prepared in example 1 of the present invention; wherein, the figure 10 (a), the figure 10 (b), the figure 10 (c), the figure 10 (d) and the figure 10 (e) are respectively three-dimensional EEM spectra after 0min,30min, 60min, 120min and 180min of bisphenol a solution absorption; FIG. 10 (f) is a graph showing the characteristic intensity variation of bisphenol a and intermediates in a three-dimensional EEM spectrum;
FIG. 11 is a graph showing the change in the removal rate of bisphenol A with pH in example 1 of the present invention; wherein FIG. 11 (a) shows the bisphenol A removal efficiency curves of example 1 of the present invention at initial pH values of 4.65, 7.0, 8.42 and 10.74, and FIG. 11 (b) shows the pH change curves of the solutions of example 1 of the present invention at initial pH values of 4.65, 7.0, 8.42 and 10.74;
FIG. 12 is a graph showing the bisphenol A removal rate as a function of catalyst loading in examples of the present invention; FIG. 12 (a) is a graph showing the removal of bisphenol A when 0.02g/L, 0.04g/L, 0.06g/L, and 0.08g/L were added in example 1 of the present invention, respectively; FIGS. 12 (b) -12 (d) are graphs showing bisphenol A removal rate change curves for the case where the amounts of the bisphenol A added in example 1 of the present invention were 0.02g/L, 0.04g/L and 0.08g/L, respectively;
FIG. 13 is a graph showing the change in the removal rate of bisphenol A with the addition of persulfate in example 1 of the present invention, wherein FIG. 13 (a) is a graph showing the removal rate of bisphenol A when 0.2mmol/L, 0.5mmol/L, 1.0mmol/L, 2.0mmol/L, respectively, are added in example 1 of the present invention; FIGS. 13 (b) -13 (d) are graphs showing the change in bisphenol A removal rate when the amount of the catalyst in example 1 of the present invention was 0.2mmol/L, 0.5mmol/L, and 2.0mmol/L, respectively;
FIG. 14 is a graph showing the change in bisphenol A removal rate in different actual water bodies according to example 1 of the present invention, wherein FIG. 14 (a) is a graph showing the removal rate of bisphenol A when DW, JAW, MYW is added to example 1 of the present invention, respectively; FIGS. 14 (b) to 14 (d) are graphs showing the change in bisphenol A removal rate when DW, JAW, MYW was added to each of example 1 of the present invention.
FIG. 15 shows the addition of 1mmol/LCl respectively in example 1 of the present invention - 、5mmol/LCl - 、 1mmol/LHCO 3 - 、1mmol/LHCO 3 - Bisphenol a removal effect graph for bisphenol a solution; wherein FIG. 15 (a) shows the addition of 1mmol/LCl in example 1 of the present invention - 、5mmol/LCl - 、1mmol/LHCO 3 - 、 1mmol/LHCO 3 - A graph of the concentration of bisphenol a in the bisphenol a solution; FIG. 15 (b) shows the addition of 1mmol/LCl in example 1 of the present invention - 、5mmol/LCl - 、1mmol/LHCO 3 - 、1mmol/LHCO 3 - A graph of bisphenol a removal rate for bisphenol a;
FIG. 16 is a graph showing the effect of bisphenol A removal when 1mg/L humic acid, 5mg/L humic acid and bisphenol A solution of example 1 of the present invention were added respectively; FIG. 16 (a) is a graph showing the concentration change of bisphenol A when 1mg/L humic acid, 5mg/L humic acid and bisphenol A solution of example 1 of the present invention were added respectively; FIGS. 16 (b) and (c) are graphs showing the removal rates of bisphenol A when 1mg/L humic acid and 5mg/L humic acid of bisphenol A solution were added in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail below with reference to the drawings and detailed description so that the above objects, features and advantages of the present invention can be more clearly understood. The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples. The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the prior art. The reagents used, as well as other instruments, are conventional reagent products available commercially, without the manufacturer's knowledge.
The applicant of the present invention found that the prior art only adopts carbon-based material loaded with nano zero-valent iron as an activated persulfate catalyst, and the effect of removing endocrine disruptors in wastewater is limited.
The invention aims to solve the problems, and provides a preparation method of a catalyst for removing endocrine disruptors, the catalyst and application of the catalyst.
In a first aspect, referring to fig. 1, fig. 1 shows a method for preparing a catalyst for removing endocrine disruptors in an embodiment of the present invention, the method comprising:
s1, preparing a B modified carbon-based material by adopting a hydrothermal method;
s2, adding deionized water into the modified carbon-based material B to dissolve the modified carbon-based material B to form a first solution, and adding ferric sulfate heptahydrate into the solution while stirring after ultrasonic treatment for 10min to form a second solution;
step S3, dropwise adding a sodium borohydride solution into the second solution at a preset dropwise adding rate under a protective atmosphere to load nano zero-valent iron on the B modified carbon-based material, and stirring for a preset time to obtain a first crude product;
and S4, repeatedly washing the first crude product by using ethanol and deionized water as detergents, and drying in a vacuum freeze dryer for a preset time to obtain the catalyst for removing endocrine disruptors.
Wherein the first solution is an aqueous solution of a B modified carbon-based material, and the B modified carbon-based material is dispersed in the solution so as to load nano zero-valent iron; the second solution is B modified carbon-based material and FeSO 4 ·7H 2 Mixed solution of O, feSO 4 ·7H 2 O is a raw material for preparing nano zero-valent iron, the first crude product is a B modified carbon-based material loaded with nano zero-valent iron, and FeSO may exist on the surface of the material 4 ·7H 2 O and NaBH 4 Is a residue of (a).
In the embodiment of the invention, the action mechanism of the B modified carbon-based material is that when the B modified carbon-based material loaded with nano zero-valent iron is mixed with persulfate, the persulfate takes unstable unpaired electrons in the B modified carbon-based material to form a metastable structure [ nZVI@BCs ]. So that [ nZVI@BCs ] have higher oxidation potential, and then [ nZVI@BCs ] fill the vacancy by capturing electrons of bisphenol A in the solution, thereby leading to oxidation of bisphenol A and providing a non-radical oxidation path for removing bisphenol A.
On the other hand, nano zero-valent iron loaded on the B modified carbon-based material can react with persulfate to obtain a free radical group with high oxidation activity, so that bisphenol A in the solution is directly oxidized, and a free radical oxidation path is provided for removing bisphenol A. According to the embodiment of the invention, the B modified carbon-based material loaded with nano zero-valent iron is used as a catalyst for removing endocrine disruptors, and the bisphenol A in the solution is removed by adopting the synergistic effect of two oxidation paths of free radical oxidation and non-free radical oxidation, so that the removal efficiency of the bisphenol A is improved.
Preferably, the method for preparing the B-modified carbon-based material by using the hydrothermal method in the step S1 includes:
s1-1, respectively weighing coffee grounds, boric acid and sodium bicarbonate, adding the coffee grounds, the boric acid and the sodium bicarbonate into deionized water, stirring the mixture at 80 ℃ for 6 hours, and then placing the mixture in an oven at 80 ℃ for drying for 12 hours;
step S1-2, placing the mixture dried in the step S1-1 into a tube furnace, heating to 800 ℃, calcining for 2 hours in a nitrogen atmosphere, and naturally cooling to room temperature to obtain a second crude product;
s1-3, grinding the geothermal crude product, cleaning the ground geothermal crude product by using ethanol and deionized water, and placing the ground geothermal crude product in a drying box at 80 ℃ for drying to obtain the B modified carbon-based material;
the invention adopts the coffee grounds as the raw materials of the carbon-based materials, has wide sources, is simple and easy to obtain, has low price, and can be widely applied to the actual wastewater treatment.
Preferably, the mass ratio of the B modified carbon-based material to the iron sulfate heptahydrate is 1:0.4-1.4.
Preferably, the concentration of the sodium borohydride solution is 10g/L; the volume ratio of the mixed solution to the sodium borohydride solution is 2:1.
Preferably, the protective atmosphere is nitrogen or inert gas atmosphere.
Preferably, the preset dripping rate is 2 drops/s, and the stirring preset time is 30 minutes.
Preferably, the mass ratio of the coffee grounds to the sodium bicarbonate to the boric acid is 5:7:0.7-2.8; the mass ratio of the coffee grounds to the deionized water is 1-5:60.
Preferably, the heating rate to 800 ℃ is 5 ℃/min.
In a second aspect, the present invention provides a catalyst for endocrine disruptor removal, the catalyst being obtained by the preparation method of any one of the first aspects, the catalyst comprising: and B modified carbon-based material and nano zero-valent iron loaded on the B modified carbon-based material.
In a third aspect, the present invention provides a method for removing endocrine disruptors, adding the catalyst of the second aspect to wastewater containing bisphenol endocrine disruptors, and simultaneously adding persulfate to remove bisphenol endocrine disruptors in the wastewater.
Preferably, the addition amount of the catalyst is 0.04-0.08g/L, the addition amount of the persulfate is 0.5-2.0mmol/L, and the initial pH value of the wastewater is 4.65-10.74.
The addition amount of the catalyst, the addition amount of persulfate and the initial pH value of the wastewater are respectively changed through a single variable experiment to determine, the addition amount of the catalyst for removing endocrine disrupters, which is prepared by the embodiment of the invention, is 0.04-0.08g/L, the addition amount of persulfate is 0.5-2.0mmol/L, and the initial pH value of the wastewater is 4.65-10.74, so that the catalyst has a better bisphenol A treatment effect.
In order to better understand the present invention, a method for preparing a catalyst for endocrine disruptor removal according to the present invention will be described with reference to a plurality of specific examples.
Example 1:
and (5) placing the collected coffee grounds into an oven at 80 ℃ for drying for 12 hours to obtain dried coffee grounds.
5g of dried coffee grounds, 7g of sodium bicarbonate and 0.7g of boric acid are respectively weighed and added into 120mL of deionized water, the obtained solution is magnetically stirred for 6 hours at 80 ℃, and then the obtained solution is placed into an oven at 80 ℃ for drying for 12 hours to obtain a mixed solid. And (3) placing the mixed solid in a tube furnace, heating to 800 ℃ at a heating rate of 5 ℃/min, calcining for 2 hours, and cooling to obtain a second crude product. And (3) grinding the obtained second crude product, washing the ground product once with ethanol, washing the ground product twice with deionized water, and drying the ground product in a drying box at 80 ℃ to obtain the B modified carbon-based material.
1.0g of the obtained B modified carbon-based material is dissolved in 100mL of deionized water, and after ultrasonic treatment is carried out for 10min, 0.4g of FeSO 4 ·7H 2 O was added to the solution and mechanically stirred for 30min. Under nitrogen atmosphere, drop-adding NaBH of 10g/L at a rate of 2 drops/s 4 50mL of solution, dropwise adding and stirring for 30min, and loading nano zero-valent iron into the B modified carbon-based material to obtain a first crude product. Repeatedly washing the first crude product with ethanol and deionized water to obtain the catalyst (nZVI@BCs) for removing endocrine disruptors.
Example 2:
and (5) placing the collected coffee grounds into an oven at 80 ℃ for drying for 12 hours to obtain dried coffee grounds.
5g of dried coffee grounds, 7g of sodium bicarbonate and 1g of boric acid are respectively weighed and added into 120mL of deionized water, the obtained solution is magnetically stirred for 6 hours at 80 ℃, and then the solution is placed into an oven at 80 ℃ for drying for 12 hours to obtain a mixed solid. And (3) placing the mixed solid in a tube furnace, heating to 800 ℃ at a heating rate of 5 ℃/min, calcining for 2 hours, and cooling to obtain a second crude product. And (3) grinding the obtained second crude product, washing the ground product once with ethanol, washing the ground product twice with deionized water, and drying the ground product in a drying box at 80 ℃ to obtain the B modified carbon-based material.
1.0g of the obtained B modified carbon-based material was dissolved in 50mL of deionized water, and after 10 minutes of ultrasound, 0.6g of FeSO was added 4 ·7H 2 O was added to the solution and mechanically stirred for 30min. Under nitrogen atmosphere, drop-adding NaBH of 10g/L at a rate of 2 drops/s 4 And (3) 25mL of solution, dropwise adding, stirring for 30min, and loading the nano zero-valent iron into the B modified carbon-based material to obtain a first crude product. Repeatedly cleaning the first crude product with ethanol and deionized water to obtain the catalyst for removing endocrine disruptors.
Example 3
And (5) placing the collected coffee grounds into an oven at 80 ℃ for drying for 12 hours to obtain dried coffee grounds.
5g of dried coffee grounds, 7g of sodium bicarbonate and 1.4g of boric acid are respectively weighed and added into 120mL of deionized water, the obtained solution is magnetically stirred for 6 hours at 80 ℃, and then the obtained solution is placed into an oven at 80 ℃ for drying for 12 hours to obtain a mixed solid. And (3) placing the mixed solid in a tube furnace, heating to 800 ℃ at a heating rate of 5 ℃/min, calcining for 2 hours, and cooling to obtain a second crude product. And (3) grinding the obtained second crude product, washing the ground product once with ethanol, washing the ground product twice with deionized water, and drying the ground product in a drying box at 80 ℃ to obtain the B modified carbon-based material.
1.0g of the obtained B modified carbon-based material was dissolved in 80mL of deionized water, and after 10min of ultrasound, 0.8g of FeSO was added 4 ·7H 2 O was added to the solution and mechanically stirred for 30min. Under nitrogen atmosphere, drop-adding NaBH of 10g/L at a rate of 2 drops/s 4 40mL of solution, dropwise adding and stirring for 30min, and loading nano zero-valent iron into the B modified carbon-based material to obtainThe first crude product. Repeatedly cleaning the first crude product with ethanol and deionized water to obtain the catalyst for removing endocrine disruptors.
Example 4
And (5) placing the collected coffee grounds into an oven at 80 ℃ for drying for 12 hours to obtain dried coffee grounds.
5g of dried coffee grounds, 7g of sodium bicarbonate and 2g of boric acid are respectively weighed and added into 120mL of deionized water, the obtained solution is magnetically stirred for 6 hours at 80 ℃, and then the solution is placed into an oven at 80 ℃ for drying for 12 hours to obtain a mixed solid. And (3) placing the mixed solid in a tube furnace, heating to 800 ℃ at a heating rate of 5 ℃/min, calcining for 2 hours, and cooling to obtain a second crude product. And (3) grinding the obtained second crude product, washing the ground product once with ethanol, washing the ground product twice with deionized water, and drying the ground product in a drying box at 80 ℃ to obtain the B modified carbon-based material.
1g of the obtained B modified carbon-based material is dissolved in 60mL of deionized water, and after ultrasonic treatment is carried out for 10min, 1.2g of FeSO 4 ·7H 2 O was added to the solution and mechanically stirred for 30min. Under nitrogen atmosphere, drop-adding NaBH of 10g/L at a rate of 2 drops/s 4 And (3) dropwise adding 30mL of the solution, stirring for 30min, and loading the nano zero-valent iron into the B modified carbon-based material to obtain a first crude product. Repeatedly cleaning the first crude product with ethanol and deionized water to obtain the catalyst for removing endocrine disruptors.
Example 5
And (5) placing the collected coffee grounds into an oven at 80 ℃ for drying for 12 hours to obtain dried coffee grounds.
5g of dried coffee grounds, 7g of sodium bicarbonate and 2.8g of boric acid are respectively weighed and added into 120mL of deionized water, the obtained solution is magnetically stirred for 6 hours at 80 ℃, and then the obtained solution is placed into an oven at 80 ℃ for drying for 12 hours to obtain a mixed solid. And (3) placing the mixed solid in a tube furnace, heating to 800 ℃ at a heating rate of 5 ℃/min, calcining for 2 hours, and cooling to obtain a second crude product. And (3) grinding the obtained second crude product, washing the ground product once with ethanol, washing the ground product twice with deionized water, and drying the ground product in a drying box at 80 ℃ to obtain the B modified carbon-based material.
1g of the obtained B modified carbon-based material is dissolved in 100mL of deionized water, and after ultrasonic treatment is carried out for 10min, 1.4g of FeSO 4 ·7H 2 O was added to the solution and mechanically stirred for 30min. Under nitrogen atmosphere, drop-adding NaBH of 10g/L at a rate of 2 drops/s 4 50mL of solution, dropwise adding and stirring for 30min, and loading nano zero-valent iron into the B modified carbon-based material to obtain a first crude product. Repeatedly cleaning the first crude product with ethanol and deionized water to obtain the catalyst for removing endocrine disruptors.
Comparative example 1
And (5) placing the collected coffee grounds into an oven at 80 ℃ for drying for 12 hours to obtain dried coffee grounds.
5g of dried coffee grounds, 7g of sodium bicarbonate and 0.7g of boric acid are respectively weighed and added into 120mL of deionized water, the obtained solution is magnetically stirred for 6 hours at 80 ℃, and then the obtained solution is placed into an oven at 80 ℃ for drying for 12 hours to obtain a mixed solid. And (3) placing the mixed solid in a tube furnace, heating to 800 ℃ at a heating rate of 5 ℃/min, calcining for 2 hours, and cooling to obtain a second crude product. And (3) grinding the obtained second crude product, washing the ground product once with ethanol, washing the ground product twice with deionized water, and then placing the ground product in a drying box at 80 ℃ for drying to obtain the B modified carbon-based materials (BCs).
Comparative example 2
And (5) placing the collected coffee grounds into an oven at 80 ℃ for drying for 12 hours to obtain dried coffee grounds.
5g of dried coffee grounds and 7g of sodium bicarbonate are respectively weighed and added into 120mL of deionized water, the obtained solution is magnetically stirred for 6 hours at 80 ℃, and then the obtained solution is placed into an oven at 80 ℃ to be dried for 12 hours to obtain a mixed solid. And (3) placing the mixed solid in a tube furnace, heating to 800 ℃ at a heating rate of 5 ℃/min, calcining for 2 hours, and cooling to obtain a second crude product. And (3) grinding the obtained second crude product, washing the ground product once with ethanol, washing the ground product twice with deionized water, and drying the ground product in a drying box at 80 ℃ to obtain the carbon-based material.
1.0g of the obtained carbon-based material was dissolved in 100mL of deionized water, and after 10 minutes of ultrasound, 0.4g of FeSO was added 4 ·7H 2 O was added to the solution and mechanically stirred for 30min. Under nitrogen atmosphere, drop-adding NaBH of 10g/L at a rate of 2 drops/s 4 50mL of the solution is dropwise added and then stirred for 30min, and the nano zero-valent iron is loaded into the carbon-based material to obtain a first crude product. The first crude product is treated with ethanol and deionized waterRepeatedly cleaning to obtain the carbon-based material (nZVI@Cs) loaded with nano zero-valent iron.
The characterization of the nZVI@BCs prepared in example 1 of the present invention is as follows:
SEM test:
the microscopic morphology of the nzvi@bcs obtained in example 1 was observed by a field emission electron microscope, and the test result is shown in fig. 2, and the result shows that the obtained nano zero-valent iron-loaded B-modified carbon-based material presents a spherical porous structure, and nano zero-valent iron is uniformly dispersed on the surface of the B-modified carbon-based material, so that bisphenol a can be adsorbed on the surface for removal.
TEM test
The nZVI@BCs obtained in the example are observed by a projection electron microscope, and the test results are shown in FIG. 3, and the results show that the round particles of the nano zero-valent iron are dispersed on a carbon base and uniformly distributed, and are consistent with the SEM test results.
XPS
Analysis of nzvi@bcs before and after the reaction was performed by XPS, and the result is shown in fig. 4, and XPS spectrum scanning shows that the catalyst contains 4 elements, the content of which is shown in table 1 below, and in the nzvi@bcs prepared in example 1 of the present invention, the mass fraction of the loaded nano zero-valent iron is 8.14%, and the mass fraction of B is 3.06%. The bond formation of the four elements before and after the reaction was analyzed, and the results are shown in FIG. 5, and FIGS. 5 (a) and (e) show (C1 s), wherein the C element is sp at the peak values of 283.11eV, 284.15eV, 285.15eV, 287.90 eV and 290.40eV, respectively 2 Carbon bond, C-H bond, C-OH or C-O-C bond, c=o bond and O-c=o bond; as shown in fig. 5 (b) and 5 (f), the oxygen in the nzvi@bcs carbon-based material is mainly distributed in three independent peaks, 530.42eV, 531.81eV and 535.63eV, respectively, C-O, C =o and Fe-O; for the B1s spectra, as shown in fig. 5 (c) and 5 (g), the two main peaks at 188.13eV and 192.30 eV correspond to interfacial hypoxia boron and boron oxide, respectively. For Fe2p, FIG. 5 (d) shows that the peak at 705.93eV corresponds to Fe 0 This confirms that the B-modified negotiable material porous carbon surface successfully supports nZVI.
TABLE 1 XPS analysis of atomic percent of C, O, B, fe elements before and after nZVI@BCs surface reaction
XRD
The results of XRD analysis of the nZVI@BCs carbon-based material before and after the reaction are shown in FIG. 6. Fig. 6 shows that the original nzvi@bcs possessed characteristic peaks at 44.70 °, 65.39 ° and 82.5 ° that were highly matched to the XRD standard pattern peaks of ZVI (pdf#06-0696), demonstrating that nZVI was successfully synthesized and attached to the BCs surface.
Adsorption removal method of nZVI@BCs on BPA:
the catalyst obtained in example 1, the modified carbon-based material B obtained in comparative example 1 and the nano zero-valent iron-supported carbon-based material obtained in comparative example 2 were respectively added to a bisphenol A solution of 0.04mmol/L, and persulfate of 1mmol/L was added thereto, and the initial pH of the three was controlled to 7.0, and an experiment was conducted at room temperature.
Experiments show that the adsorption of the nZVI@BCs to the BPA basically reaches equilibrium within 30 minutes, so that the reaction time of the adsorption experiment is set to be 30 minutes, and then the experimental data are fitted by adopting a quasi-primary dynamics model, a quasi-secondary dynamics model and a particle internal diffusion model. The kinetic model fitting and equilibrium state data thereof are shown in fig. 7 and table 2 below, and according to the analysis of the correlation coefficient R2, the fitting of the quasi-second-order kinetic model is better, the correlation coefficient is 0.999, and the correlation coefficient is closer to 1.0 than the first-order kinetic model and the intra-particle diffusion model. The results show that the quasi-secondary kinetic model is most suitable for describing the adsorption kinetics of nZVI@BCs to BPA, and also show that the adsorption of nZVI@BCs to BPA is mainly chemical adsorption.
TABLE 2 kinetic parameters of adsorption of BPA by nZVI@BCs
Adsorption isotherm data were analyzed by introducing Langmuir and Freundlich adsorption isotherm models. Adsorption isotherm model fitting and data thereof as shown in fig. 8 and table 3 below, the linear form of R2 of the Langmuir model was closer to 1.0 than the Freundlich model, indicating that adsorption of BPA by nzvi@bcs occurred as a monolayer adsorption on a uniform surface of approximately energy.
TABLE 3 adsorption isotherm parameters for adsorption of BPA by nZVI@BCs
The nZVI@BCs obtained in example 1 of the invention are compared with the BCs obtained in comparative example 1 and the nZVI@Cs obtained in comparative example 2 in degradation effect:
the catalyst obtained in example 1, the modified carbon-based material B obtained in comparative example 1 and the nano zero-valent iron-supported carbon-based material obtained in comparative example 2 were respectively added to a bisphenol A solution of 0.04mmol/L, and persulfate of 1mmol/L was added thereto, and the initial pH of the three was controlled to 7.0, and an experiment was conducted at room temperature.
The experimental results are shown in FIG. 9 (a), and the results show that the catalyst obtained in example 1 of the present invention has a removal rate of bisphenol A by persulfate of 43.1% after 30min of persulfate addition, while comparative examples 1 and 2 have 55.7% and 23.5% respectively, and the catalyst obtained in example 1 of the present invention has a removal rate of bisphenol A by persulfate of nearly 100% after 60min of persulfate addition, while comparative examples 1 and 2 have only 76.6% and 35.5%.
The removal effect of bisphenol A before and after the reaction of the three catalysts and persulfate was measured, and the total organic carbon concentration in the system before and after the reaction was measured, and as shown in FIG. 9 (b), the total organic carbon removal rate of bisphenol A was 70.41% in the solution added to the catalyst obtained in example 1, whereas the total organic carbon removal rate of bisphenol A was only 32.42% and 16.09% in the solutions added to comparative examples 1 and 2. Therefore, the catalyst for endocrine disruption removal prepared by the embodiment of the invention can directly oxidize most bisphenol A into carbon dioxide and water in the removal process, and decompose the carbon dioxide and the water into inorganic matters harmless to water, so that the catalyst has a good application prospect in wastewater treatment.
The effectiveness of mixing nzvi@bcs and persulfate to remove bisphenol a was verified:
experiments were carried out at room temperature by adding the nZVI@BCs obtained in example 1 to a bisphenol A solution added at 0.04mmol/L, adsorbing for 30min, adding 1mmol/L persulfate, and controlling the initial pH of the three to 7.0. The fluorescence spectra of bisphenol A and bisphenol A intermediate products in the solution are researched by adopting a three-dimensional EEM fluorescence spectrum, the result is shown in fig. 10, fig. 10 (a) shows that the initial bisphenol A solution has obvious fluorescence characteristic peaks of phenol functional groups, the fluorescence intensity of the fluorescence peaks of the phenol characteristic peaks is reduced after adsorption for 30min, the fluorescence intensity of the bisphenol A is gradually weakened after persulfate is added, the fluorescence peak at the other position is rapidly enhanced and weakened, the reaction time is further prolonged to 180min, and the fluorescence signals of the bisphenol A and the intermediate products are gradually weakened, as shown in fig. 10 (c) - (e), the result shows that most of bisphenol A is destroyed or mineralized. From the results of fig. 10 (f), it was shown that the fluorescence intensity of bisphenol a gradually decreased, while the fluorescence intensity of the intermediate product was first increased and then decreased, verifying the effectiveness of mixing nzvi@bcs and persulfate to remove bisphenol a.
The conditions of use of the nzvi@bcs prepared in example 1 were evaluated as follows:
pH conditions of use:
controlling the concentration of bisphenol A in water to be 0.04mmol/L, adding 0.06g/L of nZVI@BCs and 1mmol/L of persulfate at room temperature, adjusting the pH values to be 4.65, 7.02, 8.42 and 10.74 respectively, and measuring the concentration change condition of bisphenol A in the solution under the four conditions.
As shown in FIG. 11 (a), the removal rate of bisphenol A is decreased and then is increased along with the increase of the pH, while FIG. 11 (b) shows that the pH of the solution is rapidly decreased after the persulfate is added, but the removal rate of bisphenol A can still reach more than 85% in the range, so that the catalyst prepared by the embodiment of the invention has better catalytic effect in a wider pH range of 4.65-10.74.
Addition amount of nzvi@bcs:
controlling the concentration of bisphenol A in water to be 0.04mmol/L, controlling the pH value of the water to be 7.00, adding 1mmol/L persulfate and respectively adding 0.02g/L, 0.04g/L, 0.06g/L and 0.08g/L nZVI@BCs at room temperature, and measuring the concentration change condition of bisphenol A in the solution under the four conditions.
As shown in the test result in FIG. 12 (a), as the addition amount of the nZVI@BCs is increased, the removal rate of bisphenol A is gradually increased, and the result shows that the higher the addition amount of the nZVI@BCs is in the range of 0.02g/L-0.08g/L, the higher the removal rate of bisphenol A is, and when the addition amount of the nZVI@BCs is up to 0.08g/L, the removal rate of bisphenol A can be up to 96.9%; FIG. 12 (b) shows that in the course of increasing the amount of nZVI@BCs added, the reaction before and after the addition of persulfate was gradually increased, indicating that the removal efficiency of bisphenol A was also improved by increasing the amount of nZVI@BCs added.
The addition amount of persulfate:
controlling the concentration of bisphenol A in a water body to be 0.04mmol/L, controlling the pH value of the water body to be 7.00, adding 0.06g/L nZVI@BCs at room temperature, adding 0.2mmol/L, 0.5mmol/L, 1.0mmol/L and 2.0mmol/L persulfates respectively, and measuring the concentration change condition of bisphenol A in the solution under the four conditions.
As shown in the test result in FIG. 13 (a), as the addition amount of persulfate increases, the removal rate of bisphenol A gradually increases, and the result shows that the higher the addition amount of persulfate is, the higher the removal rate of bisphenol A is, and when the addition amount of persulfate is 2.0mmol/L, the removal rate of bisphenol A can reach 100%; fig. 13 (b) shows that the reaction rate after the addition of persulfate was gradually increased in the course of gradually increasing the addition amount of persulfate, indicating that the addition amount of persulfate was increased and the removal efficiency of bisphenol a was also improved.
The nZVI@BCs prepared in the embodiment are used for removing endocrine disruptors in an actual water body, and the test results are as follows:
adding 0.04g/L of nZVI@BCs into a water body, controlling the initial concentration of bisphenol A in the water body to be 0.07mmol/L, and measuring the concentration of bisphenol A in three actual water bodies, wherein the pH value at room temperature is 7.0. The test results are shown in fig. 14, and the BPA removal rates in three actual waters RW, JAW and MYW are 85.47%, 74.40% and 76.95%, respectively. Experiments prove that the catalyst for removing endocrine disruptors prepared by the embodiment of the invention still has a good catalytic effect in water body with various ions and organic matter interferences, has a bisphenol A removal rate of more than 74 percent, and has a good practical application prospect.
The influence factors for the removal of endocrine disruptors in an actual body of water for nZVI@BCs were tested as follows:
anionic influence:
0.06g/L of nZVI@BCs was added to a solution containing 1mmol/LCl, respectively - 、5mmol/LCl - 、 1mmol/LHCO 3 - 、1mmol/LHCO 3 - In the bisphenol A solution, the initial concentration of bisphenol A in the water body is controlled to be 0.07mmol/L, the pH value at room temperature is 7.0, and the concentration change of bisphenol A in the water body is measured.
The test results are shown in FIG. 15, with Cl - The apparent rate of the first stage of the nZVI@BCs/PS system was significantly faster with increasing the dosage from 0mM to 5mM, possibly due to the excess of negatively charged Cl - Electrons can also be supplied to PS, producing excess active chloride and sulfate to participate in the BPA degradation process. When Cl - Change to HCO 3 - When the inhibitor is used, the inhibition effect is obvious, and HCO 3 - Has obvious inhibition effect on absorption and degradation of BPA of nZVI@BCs/PS system, and the inhibition effect is along with HCO 3 - The increase in concentration is enhanced.
Humic acid effect:
0.06g/L nZVI@BCs are respectively added into bisphenol A solution containing 1mg/L humic acid and 5mg/L humic acid, the initial concentration of bisphenol A in the water body is controlled to be 0.07mmol/L, the pH value at room temperature is 7.0, and the change of the concentration of bisphenol A in the water body is measured.
The test results are shown in fig. 16 (a), and the removal rate of bisphenol a is significantly reduced with the increase of the concentration of added humic acid, while according to fig. 16 (b), the reaction rate during the removal is significantly lower than that of the control group without humic acid, because various organic matters in humic acid can compete with bisphenol a for pores and competing consumption of free radicals as indicated by carbon-based materials of nzvi@bcs, thereby reducing the rate of adsorption and oxidative degradation thereof.
According to the test in the embodiment, the catalyst for removing endocrine disruptors prepared in the embodiment of the invention has a good removing effect in the pH range of 4.65-10.74, and the removing rate of the catalyst for removing endocrine disruptors prepared in the embodiment of the invention is still 74% when the catalyst for removing endocrine disruptors is applied to an actual water body. Therefore, the B modified carbon-based material prepared by the embodiment of the invention can be applied to actual water bodies and has a good removal effect.
For the purposes of simplicity of explanation, the methodologies are shown as a series of acts, but one of ordinary skill in the art will recognize that the present invention is not limited by the order of acts described, as some acts may, in accordance with the present invention, occur in other orders and concurrently. Further, those skilled in the art will recognize that the embodiments described in the specification are all of the preferred embodiments, and that the acts and components referred to are not necessarily required by the present invention.
The preparation method, the catalyst and the application of the catalyst for removing endocrine disruptors provided by the invention are described in detail, and specific examples are used for describing the principle and the implementation of the invention, and the description of the examples is only used for helping to understand the method and the core idea of the invention; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present invention, the present description should not be construed as limiting the present invention in view of the above.

Claims (9)

1. A method of preparing a catalyst for endocrine disruptor removal, the method comprising:
step 1, preparing a B modified carbon-based material by adopting a hydrothermal method;
step 2, adding deionized water into the modified carbon-based material B to dissolve the modified carbon-based material B to form a first solution, and adding ferric sulfate heptahydrate into the solution while stirring after ultrasonic treatment for 10min to form a second solution;
step 3, dropwise adding sodium borohydride solution into the second solution at a preset dropwise adding rate under a protective atmosphere to load nano zero-valent iron on the B modified carbon-based material, and stirring for a preset time to obtain a first crude product;
step 4, repeatedly washing the first crude product by using ethanol and deionized water as detergents, and drying in a vacuum freeze dryer for a preset time to obtain the catalyst for removing endocrine disruptors;
the method for preparing the B modified carbon-based material by adopting the hydrothermal method in the step 1 comprises the following steps:
step 1-1, respectively weighing coffee grounds, boric acid and sodium bicarbonate, adding the coffee grounds, the boric acid and the sodium bicarbonate into deionized water, stirring the mixture at 80 ℃ for 6 hours, and then placing the mixture into an oven at 80 ℃ for drying for 12 hours;
step 1-2, placing the mixture dried in the step 1-1 into a tube furnace, heating to 800 ℃, calcining for 2 hours in nitrogen atmosphere, and naturally cooling to room temperature to obtain a second crude product;
and 1-3, grinding the second crude product, cleaning with ethanol and deionized water, and placing in a drying box at 80 ℃ for drying to obtain the B modified carbon-based material.
2. The method for preparing a catalyst for endocrine disruptor removal according to claim 1, wherein a mass ratio of the B-modified carbon-based material and the iron sulfate heptahydrate is 1:0.4-1.4.
3. The method for preparing a catalyst for endocrine disruptor removal according to claim 1, wherein the concentration of the sodium borohydride solution is 10g/L; the volume ratio of deionized water to sodium borohydride solution in the step 2 is 2:1; the protective atmosphere is nitrogen or inert gas atmosphere.
4. The method for preparing a catalyst for endocrine disruptor removal according to claim 1, wherein the preset dropping rate is 2 drops/s and the stirring preset time is 30 minutes.
5. The method for preparing the catalyst for removing endocrine disruptors according to claim 1, wherein the mass ratio of the coffee grounds to sodium bicarbonate to boric acid is 5:7:0.7-2.8; the mass ratio of the coffee grounds to the deionized water is 1-5:60.
6. The method for preparing a catalyst for endocrine disruptor removal according to claim 1, wherein the heating rate to 800 ℃ is 5 ℃/min.
7. A catalyst for endocrine disruptor removal, wherein the catalyst is obtained by the method of any one of the preceding claims 1-6, the catalyst comprising: and B modified carbon-based material and nano zero-valent iron loaded on the B modified carbon-based material.
8. A method of removing endocrine disruptors, the method comprising: a method for removing bisphenol endocrine disruptors in wastewater comprising adding the catalyst of claim 7 to wastewater containing bisphenol endocrine disruptors and adding persulfate.
9. The method for removing endocrine disruptors according to claim 8, wherein the catalyst is added in an amount of 0.04-0.08g/L, the persulfate is added in an amount of 0.5-2.0mmol/L, and the initial pH of the wastewater is 4.65-10.74.
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