CN114671510A - Method for degrading antibiotics by activating persulfate through Fe-N self-doped algae-based carbon catalyst - Google Patents
Method for degrading antibiotics by activating persulfate through Fe-N self-doped algae-based carbon catalyst Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 101
- 241000195493 Cryptophyta Species 0.000 title claims abstract description 82
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- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 51
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- 238000000034 method Methods 0.000 title claims abstract description 42
- 230000003213 activating effect Effects 0.000 title claims abstract description 30
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- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 claims description 11
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- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
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- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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Abstract
The invention discloses a method for degrading antibiotics by activating persulfate through a Fe-N self-doping algae-based carbon catalyst, which is characterized in that the antibiotics are degraded by taking the Fe-N self-doping algae-based carbon catalyst as a catalyst for activating persulfate, wherein the Fe-N self-doping algae-based carbon catalyst is prepared by taking anabaena as a raw material and taking soluble carbonate as a pore-forming agent and calcining the raw material at the temperature of more than 600 ℃. The method takes the Fe-N self-doping algae-based carbon catalyst with the advantages of large specific surface area, many reaction active sites, high catalytic activity and the like as the catalyst, can effectively activate persulfate and convert the persulfate into active groups with strong oxidation effect on antibiotics, can realize effective degradation of the antibiotics by utilizing the active groups, has the advantages of simple process, convenient operation, low cost, good degradation effect and the like, has better degradation effect on various antibiotics, and has high use value and good application prospect.
Description
Technical Field
The invention belongs to the technical field of material preparation and environmental catalysis, and relates to a method for degrading antibiotics by activating persulfate through a Fe-N self-doped algae-based carbon catalyst.
Background
Antibiotics are used as an effective bacteriostatic agent and widely applied to human medical treatment and livestock breeding, but the abundant application scenes also provide various ways for the discharge of antibiotic-polluted wastewater, and increase the environmental exposure risk. In the past decades, the pollution of antibiotic-polluted wastewater is more and more serious, and trace antibiotics can be detected in natural water bodies even drinking water, thereby generating great threat to aquatic organisms and human health. Traditional sewage treatment techniques have limited treatment of antibiotic wastewater due to their non-biochemical nature. The persulfate-based advanced oxidation technology proves to be an ideal new way, and the persulfate can be converted into SO with high oxidation-reduction potential under certain activation conditions4 ·-Thereby realizing the degradation and mineralization of organic pollutants. The SO-based oxidation described above compares to the OH-based Fenton advanced oxidation technique4 ·-The advanced oxidation technology has wider application range to pH, higher oxidation-reduction potential of active substances and long service life. The single persulfate has no oxidizing capability and needs to be activated under certain conditions, and the transition metal-based catalyst is proved to have good catalytic activity, but the problem of metal leaching inevitably occurs in the use process, so that secondary pollution is caused. Biochar is a non-metallic material derived from biomass, has the advantages of biocompatibility, environmental friendliness, low price, wide source and the like, and is widely applied to the fields of environmental adsorption, environmental catalysis and the like. However, the catalytic activity of conventional biochar is limited. Therefore, how to provide the persulfate biochar catalyst with high catalytic activity has important significance for improving the application of persulfate-based advanced oxidation technology in the field of environmental remediation and treatment.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for degrading antibiotics by activating persulfate through a Fe-N self-doped algae-based carbon catalyst, which has the advantages of simple process, convenience in operation, low cost and good degradation effect.
In order to solve the technical problems, the invention adopts the following technical scheme.
A method for degrading antibiotics by activating persulfate through a Fe-N self-doped algae-based carbon catalyst comprises the following steps of performing degradation treatment on antibiotics by taking the Fe-N self-doped algae-based carbon catalyst as a catalyst for activating persulfate; the Fe-N self-doped algae-based carbon catalyst is prepared by calcining anabaena as a raw material and soluble carbonate as a pore-forming agent; the temperature of the calcination is greater than 600 ℃.
The method for degrading the antibiotics by activating the persulfate through the Fe-N self-doped algae-based carbon catalyst is further improved, and the calcining temperature is 650-800 ℃.
In a further improvement of the method for degrading antibiotics by activating persulfate through the Fe-N self-doping algal-based carbon catalyst, the preparation method of the Fe-N self-doping algal-based carbon catalyst comprises the following steps:
s1, mixing anabaena and soluble carbonate, and performing ball milling to obtain a mixture;
s2, calcining the mixture obtained in the step S1, and washing with water to obtain the Fe-N self-doping algae-based carbon catalyst.
In the step S1, the mass ratio of the anabaena to the soluble carbonate is 1: 0.5-1.5; the soluble carbonate is potassium carbonate and/or sodium carbonate.
In the above method for degrading antibiotics by activating persulfate through the Fe-N self-doped algae-based carbon catalyst, the rotation speed of the ball mill is 300r/min to 350r/min in step S1; the ball milling time is 20 min-30 min.
In the step S2, the temperature rise rate in the calcination process is 5-15 ℃/min; the calcining time is 2-5 h; and the water washing is to wash the calcined product with ultrapure water until the filtrate is neutral.
The method for degrading antibiotics by activating persulfate through the Fe-N self-doping algae-based carbon catalyst is further improved, and the method for degrading antibiotics in the water body by taking the Fe-N self-doping algae-based carbon catalyst as the catalyst for activating persulfate comprises the following steps: mixing and stirring the Fe-N self-doped algae-based carbon catalyst and the antibiotic wastewater, and adding persulfate to perform a catalytic degradation reaction to complete the degradation of the antibiotic in the wastewater.
The method for degrading the antibiotics by activating the persulfate through the Fe-N self-doping algae-based carbon catalyst is further improved, wherein the mass ratio of the Fe-N self-doping algae-based carbon catalyst to the antibiotics in the wastewater is 5-15: 1; the addition amount of the persulfate is 1-5 mmol of persulfate added in each liter of antibiotic wastewater.
According to the method for degrading the antibiotics by activating the persulfate through the Fe-N self-doped algae-based carbon catalyst, the antibiotics in the antibiotic wastewater are sulfonamides; the sulfonamide antibiotics are sulfamethoxazole or sulfadimidine; the initial concentration of the antibiotics in the antibiotic wastewater is less than or equal to 80 mg/L; the persulfate is peroxydisulfate or peroxymonosulfate.
The method for degrading antibiotics by activating persulfate through the Fe-N self-doped algae-based carbon catalyst is further improved, wherein the stirring time is 0.5-2 h; the time of the catalytic degradation reaction is 40 min-100 min.
Compared with the prior art, the invention has the advantages that:
(1) aiming at the defects of small specific surface area, few reaction active sites, poor catalytic activity and the like of the existing biochar catalyst, and the defects that the biochar catalyst is difficult to effectively activate persulfate so as to be difficult to effectively degrade antibiotics and the like, the invention creatively provides a method for degrading antibiotics by using Fe-N self-doped algae-based carbon catalyst to activate persulfate, wherein the Fe-N self-doped algae-based carbon catalyst is used as a catalyst for activating persulfate to degrade antibiotics, and is prepared by using fish algae as a raw material and soluble carbonate as an fishy-forming agent and calcining at the temperature of more than 600 ℃. According to the invention, anabaena is used as a raw material, contains abundant nitrogen elements and trace iron elements, is calcined to form the Fe and N self-doped algae-based carbon catalyst, has the advantages of large specific surface area, more reaction active sites, high catalytic activity and the like, and meanwhile, as part of Fe-N or N active sites redistribute surrounding carbon network electrons, the shuttle of electrons is accelerated, SO that persulfate is activated on a carbon-based material, and the persulfate can be converted into SO with high redox potential4 ·-Thereby utilizing SO4 ·-The strong oxidation effect of the antibiotic realizes the degradation and mineralization of the antibiotic. The method for degrading the antibiotics by activating the persulfate through the Fe-N self-doped algae-based carbon catalyst can realize effective degradation of the antibiotics, has the advantages of simple process, convenience in operation, low cost, good degradation effect and the like, has a good degradation effect on various antibiotics, and is high in use value and high in application value before applicationThe scene is good.
(2) In the invention, the mixture of anabaena and soluble carbonate is calcined at the temperature of 650-800 ℃, which is more beneficial to the conversion of amorphous carbon in the biochar to graphite carbon configuration in the high-temperature calcination process to form an ordered graphite structure and provide a matrix for electron transmission; meanwhile, under the temperature condition, the conversion of pyridine N and pyrrole N to graphite N changes the surface charge distribution of the carbon material, forms a nitrogen negative charge center and a surrounding carbon positive charge structure, and generates an Fe-N structure to provide active sites for the adsorption of organic matters and the activation of persulfate. However, if the calcination temperature is too high, the microporous structure of the biochar is likely to collapse, so that the specific surface area is reduced, which is not favorable for exposing the active sites of the biochar. And the calcination temperature is too low, the graphitization degree of the carbon structure is low, and the transmission of electrons is not facilitated.
(3) According to the invention, the soluble carbonate and the anabaena are contacted on a molecular level through mechanical ball milling, conditions are provided for optimizing a biological carbon pore channel structure in a subsequent high-temperature calcination process, and the calcination is carried out after the ball milling, so that the preparation of the Fe-N self-doped algae-based carbon catalyst with the ultrahigh specific surface area is more favorable for preparing the Fe-N self-doped algae-based carbon catalyst with the ultrahigh specific surface area.
(4) In the invention, the Fe-N self-doped algae-based carbon catalyst is used for treating the antibiotic wastewater, so that the resource utilization of algae organic matters is realized, the treatment pressure of offshore eutrophication is favorably reduced, and the environmental treatment cost is reduced; on the other hand, a way is provided for the degradation of antibiotics in the actual water body, and the treatment of wastes with processes of wastes against each other is really realized.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
FIG. 1 is an XPS graph of an Fe-N self-doping algal based carbon catalyst (FNB-1) prepared in example 1 of the present invention.
FIG. 2 is a Raman spectrum of the Fe-N self-doping algal based carbon catalyst (FNB-1, FNB-2, FNB-3) prepared in example 1 of the present invention.
FIG. 3 is a graph showing the time-degradation efficiency of the sulfamethoxazole solution degraded by the Fe-N self-doping algal-based carbon catalysts (FNB-1, FNB-2, FNB-3, FNB-4, FNB-5) and the spirulina-based carbon catalyst (SB) in example 1 of the present invention.
FIG. 4 is a graph of time-degradation efficiency when PMS is activated by Fe-N self-doped algae-based carbon catalyst (FNB-1) and sulfamethoxazole solution is degraded by PDS in example 1 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention. The materials and equipment used in the following examples are commercially available.
Example 1
A method for degrading antibiotics by activating persulfate through a Fe-N self-doped algae-based carbon catalyst, specifically, performing degradation treatment on antibiotics in a water body by taking the Fe-N self-doped algae-based carbon catalyst as a catalyst for activating persulfate, comprises the following steps:
taking Fe-N self-doped algae-based carbon catalysts (FNB-1, FNB-2, FNB-3, FNB-4 and FNB-5) and spirulina-based carbon catalysts (SB), respectively placing 5mg of the Fe-N self-doped algae-based carbon catalysts and the spirulina-based carbon catalysts in sulfamethoxazole solution with the concentration of 10mg/L, stirring for 30 minutes to reach adsorption balance, then adding 0.1mL of peroxydisulfate (PDS, specifically sodium persulfate) solution with the concentration of 0.5M to perform catalytic degradation reaction, and finishing degradation of organic pollutants in water.
In the embodiment, the degradation effect of the Fe-N self-doped algae-based carbon catalyst (FNB-1) on sulfamethoxazole is also considered when the persulfate is peroxymonosulfate (PMS, specifically potassium hydrogen persulfate).
In this embodiment, the Fe-N self-doping algae-based carbon catalyst (FNB-1) is prepared from anabaena as a raw material, and includes the following steps:
directly mixing 10.0g of anabaena and 10.0g of anhydrous potassium carbonate in an agate tank, mechanically ball-milling for 30min under the condition that the rotating speed is 300r/min, and then putting the mixture into a tubular furnace for pyrolysis. In N2In the atmosphere, the temperature is raised to 700 ℃ at the speed of 10 ℃/min and the temperature is kept for 2h for calcination. And after natural cooling, taking out the product, fully grinding, and washing for 3 to 4 times by using ultrapure water until the filtrate is neutral. And then drying and grinding the filtered product in an oven to obtain the Fe-N self-doping algae-based carbon catalyst which is named as FNB-1.
In this embodiment, the Fe-N self-doping algae-based carbon catalyst (FNB-2) is prepared from anabaena as a raw material, and includes the following steps:
directly mixing 10.0g of anabaena and 10.0g of anhydrous potassium carbonate in an agate tank, mechanically ball-milling for 30min under the condition that the rotating speed is 300r/min, and then putting the mixture into a tubular furnace for pyrolysis. In N2In the atmosphere, the temperature is raised to 600 ℃ at the speed of 10 ℃/min and the temperature is kept for 2h for calcination. And after natural cooling, taking out the product, fully grinding, and washing for 3 to 4 times by using ultrapure water until the filtrate is neutral. And then drying and grinding the filtered product in an oven to obtain the Fe-N self-doping algae-based carbon catalyst which is named as FNB-2.
In this embodiment, the Fe-N self-doping algae-based carbon catalyst (FNB-3) is prepared from anabaena as a raw material, and includes the following steps:
directly mixing 10.0g of anabaena and 10.0g of anhydrous potassium carbonate in an agate tank, mechanically ball-milling for 30min under the condition that the rotating speed is 300r/min, and then putting the mixture into a tubular furnace for pyrolysis. In N2In the atmosphere, the temperature was raised to 500 ℃ at a rate of 10 ℃/min and the temperature was maintained for 2 hours to perform calcination. And after natural cooling, taking out the product, fully grinding, and washing for 3 to 4 times by using ultrapure water until the filtrate is neutral. And then drying and grinding the filtered product in an oven to obtain the Fe-N self-doping algae-based carbon catalyst which is named as FNB-3.
In this embodiment, the Fe-N self-doping algae-based carbon catalyst (FNB-4) is prepared from anabaena as a raw material, and includes the following steps:
10.0g of anabaena is taken out and dissolved in 100mL of ultrapure water in an agate tank, the mixture is continuously stirred for 12h, after the mixture is fully mixed, the mixture is placed in an oven at 85 ℃ for drying for 24h until being dried, and then the mixture is placed in a tubular furnace for pyrolysis. In N2In the atmosphere, the temperature is raised to 700 ℃ at the speed of 10 ℃/min and the temperature is kept for 2h for calcination. And after natural cooling, taking out the product, fully grinding, and washing for 3 to 4 times by using ultrapure water until the filtrate is neutral. And then drying and grinding the filtered product in an oven to obtain the Fe-N self-doping algae-based carbon catalyst which is named as FNB-4.
In this embodiment, the Fe-N self-doping algae-based carbon catalyst (FNB-5) is prepared from anabaena as a raw material, and includes the following steps:
10.0g of anabaena is taken to be put in an agate tank, mechanically ball milled for 30min under the condition of the rotating speed of 300r/min, and then put in a tube furnace for pyrolysis. At N2In the atmosphere, the temperature is raised to 700 ℃ at the speed of 10 ℃/min and the temperature is kept for 2h for calcination. After natural cooling, the black powder is taken out, fully ground and added with 100mL of 0.5M sulfuric acid solution, and soaked for 12 h. And (3) washing with ultrapure water for 3-4 times until the filtrate is neutral, then placing the filtered material in an oven for drying and grinding to obtain the Fe-N self-doped algae-based carbon catalyst, which is named as FNB-5.
In this embodiment, the adopted spirulina-based carbon catalyst (SB) is prepared from spirulina as a raw material, and includes the following steps:
10.0g of spirulina and 10.0g of anhydrous potassium carbonate are directly mixed in an agate tank, mechanically ball-milled for 30min under the condition of the rotating speed of 300r/min, and then placed in a tube furnace for pyrolysis. In N2In the atmosphere, the temperature is raised to 700 ℃ at the speed of 10 ℃/min and the temperature is kept for 2h for calcination. And after natural cooling, taking out the product, fully grinding, and washing for 3 to 4 times by using ultrapure water until the filtrate is neutral. And then putting the filtered product into an oven for drying and grinding to obtain the spirulina-based carbon catalyst named as SB.
FIG. 1 is an XPS graph of an Fe-N self-doping algal based carbon catalyst (FNB-1) prepared in example 1 of the present invention. As can be seen from FIG. 1, the Fe-N self-doping algal based carbon catalyst (FNB-1) of the present invention is doped with Fe and N, which shows that the Fe-N self-doping algal based carbon catalyst has been successfully prepared. In addition, according to the test results of the elements Mapping, SEM, TEM, EDS and the like, the Fe-N self-doped algae-based carbon catalyst (FNB-1) has a porous Fe-N co-doped algae-based carbon and shows a sponge-like structure with developed pores. Meanwhile, EDS and element Mapping results also show that the Fe-N self-doping algae-based carbon catalyst (FNB-1) is doped with Fe and N and is uniformly distributed on a carbon material, which also indicates that the Fe-N self-doping algae-based carbon catalyst is successfully synthesized.
Table 1 shows data on pore structures of Fe-N self-doping algal based carbon catalysts (FNB-1, FNB-2, FNB-3) prepared in example 1 of the present invention
As can be seen from Table 1, when the pyrolysis temperature is raised from 500 ℃ to 600 ℃, the surface area and the total pore volume of the Fe-N self-doping algae-based carbon catalyst are increased, the specific surface area of FNB-2 is the largest and is almost 3 times of FNB-3, and the specific surface area reaches 945.43m2g-1At this time, the micropore volume is larger than the mesopore volume, and the average pore diameter is reduced from 2.42nm to 2.25 nm. When the pyrolysis temperature is increased to 700 ℃, the specific surface area is slightly reduced, the volume of the micropores is smaller than that of the mesopores, which indicates that micropores are mainly formed at the low pyrolysis temperature, and when the activation temperature is higher, the mesopore content is increased, so that the specific surface area is reduced. Therefore, compared with Fe-N self-doping algae-based carbon catalysts (FNB-2 and FNB-3), the Fe-N self-doping algae-based carbon catalyst (FNB-1) has a larger specific surface area, and a mesoporous structure is richer, so that more sites can be provided for adsorption of pollutants and activation of the catalyst, and when the catalyst is used for treating antibiotic wastewater, the effective removal of antibiotics is more favorably realized.
FIG. 2 shows Fe-N autodoped algae obtained in example 1 of the present inventionRaman spectra of the carbon-based catalysts (FNB-1, FNB-2, FNB-3). As can be seen from FIG. 2, all samples had two typical peaks, located approximately at 1340cm-1And 1580cm-1Respectively belonging to the D peak and the G peak of the carbon material. The D peak is generally caused by an unordered sp2 carbon defect, while the G peak is associated with a highly ordered graphitic carbon structure with a tangential stretching mode. The D peak, the G peak, has a peak intensity ratio I as the pyrolysis temperature increases from 500 ℃ to 700 DEG CD/IGThe reduction to 1.74 indicates that more graphitic carbon structures are formed during annealing, which is beneficial to the transfer and transmission of electrons. Therefore, compared with Fe-N self-doping algae-based carbon catalysts (FNB-2 and FNB-3), the Fe-N self-doping algae-based carbon catalyst (FNB-1) has a graphitized carbon structure with higher graphitization degree, namely graphite N doping and Fe-N structures, and provides higher reaction active sites for activating persulfate.
Sampling at each period of time in the catalytic degradation reaction process, testing the concentration of sulfamethoxazole in the solution, and calculating to obtain the degradation effect of different catalysts on sulfamethoxazole under different time conditions.
FIG. 3 is a graph showing the time-degradation efficiency of the sulfamethoxazole solution degraded by the Fe-N self-doping algal-based carbon catalysts (FNB-1, FNB-2, FNB-3, FNB-4, FNB-5) and the spirulina-based carbon catalyst (SB) in example 1 of the present invention. As can be seen from FIG. 3, the adsorption performance and the catalytic activity of the Fe-N self-doping algae-based carbon catalysts (FNB-1, FNB-2 and FNB-3) are remarkably different, which indicates that the calcination temperature has an important influence on the performance regulation of the biochar. Compared with the degradation performance of the Fe-N self-doped algae-based carbon catalyst (FNB-1) and the Fe-N self-doped algae-based carbon catalyst (FNB-4 and FNB-5), the full contact between algae and carbonate on a molecular level layer can be realized by adopting mechanical ball milling, so that active sites can be better exposed, and the loss of metal sites can be better prevented by washing, so that the excellent degradation performance is maintained. Compared with the spirulina based carbon catalyst (SB), the anabaena used in the experiment has higher iron content in terms of components, thereby exposing more Fe-N active sites to participate in the degradation of sulfamethoxazole. The results show that the Fe-N self-doping algae-based carbon catalyst (FNB-1) has good capacity of activating persulfate, and can effectively remove organic pollutants in water.
FIG. 4 is a graph of time-degradation efficiency when PMS is activated by Fe-N self-doped algae-based carbon catalyst (FNB-1) and sulfamethoxazole solution is degraded by PDS in example 1 of the present invention. As shown in the degradation data of FIG. 4, the Fe-N self-doped algae-based carbon catalyst (FNB-1) can effectively degrade organic pollutants in the presence of PMS and PDS, which indicates that the Fe-N self-doped algae-based carbon catalyst (FNB-1) has excellent activation capability on both PMS and PDS.
The results show that the Fe-N self-doped algae-based carbon catalyst prepared by the invention has the advantages of high specific surface area, more reactive active sites and the like, can be widely used for degrading antibiotics, can obtain better degradation effect, and has good application value and application prospect.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make many possible variations and modifications to the disclosed embodiments, or equivalent modifications, without departing from the spirit and scope of the invention, using the methods and techniques disclosed above. Therefore, any simple modifications, equivalent substitutions, equivalent changes and modifications made to the above embodiments according to the technical essence of the present invention are within the scope of the technical scheme of the present invention.
Claims (10)
1. A method for degrading antibiotics by activating persulfate through a Fe-N self-doping algae-based carbon catalyst is characterized in that the Fe-N self-doping algae-based carbon catalyst is used as a catalyst for activating persulfate to degrade the antibiotics; the Fe-N self-doped algae-based carbon catalyst is prepared by calcining anabaena as a raw material and soluble carbonate as a pore-forming agent; the temperature of the calcination is greater than 600 ℃.
2. The method for activating the persulfate so as to degrade the antibiotics by using the Fe-N self-doped algae-based carbon catalyst according to claim 1, wherein the calcining temperature is 650-800 ℃.
3. The method for activating the persulfate degradation antibiotics by using the Fe-N self-doped algae-based carbon catalyst according to claim 2, wherein the preparation method of the Fe-N self-doped algae-based carbon catalyst comprises the following steps:
s1, mixing anabaena and soluble carbonate, and performing ball milling to obtain a mixture;
s2, calcining the mixture obtained in the step S1, and washing with water to obtain the Fe-N self-doping algae-based carbon catalyst.
4. The method for degrading antibiotics by using Fe-N self-doped algae-based carbon catalyst activated persulfate as claimed in claim 3, wherein in step S1, the mass ratio of the anabaena and the soluble carbonate is 1: 0.5-1.5; the soluble carbonate is potassium carbonate and/or sodium carbonate.
5. The method for activating the persulfate so as to degrade the antibiotics by using the Fe-N self-doped algae-based carbon catalyst according to claim 4, wherein in the step S1, the rotation speed of the ball mill is 300r/min to 350 r/min; the ball milling time is 20 min-30 min.
6. The method for activating the persulfate and degrading the antibiotics by using the Fe-N self-doped algae-based carbon catalyst according to claim 5, wherein in the step S2, the temperature rise rate in the calcining process is 5 ℃/min to 15 ℃/min; the calcining time is 2-5 h; and the water washing is to wash the calcined product with ultrapure water until the filtrate is neutral.
7. The method for degrading antibiotics by using the Fe-N self-doped algae-based carbon catalyst activated persulfate as claimed in any one of claims 1 to 6, wherein the Fe-N self-doped algae-based carbon catalyst is used as the catalyst for activating persulfate to carry out degradation treatment on the antibiotics in the water body, and comprises the following steps: mixing and stirring the Fe-N self-doped algae-based carbon catalyst and the antibiotic wastewater, and adding persulfate to perform a catalytic degradation reaction to complete the degradation of the antibiotic in the wastewater.
8. The method for degrading antibiotics by using the Fe-N self-doping algae-based carbon catalyst activated persulfate as claimed in claim 7, wherein the mass ratio of the Fe-N self-doping algae-based carbon catalyst to the antibiotics in the wastewater is 5-15: 1; the addition amount of the persulfate is 1-5 mmol of persulfate added in each liter of antibiotic wastewater.
9. The method for activating the persulfate so as to degrade the antibiotics by using the Fe-N self-doped algae-based carbon catalyst according to claim 8, wherein the antibiotics in the antibiotic wastewater are sulfanilamide antibiotics; the sulfonamide antibiotics are sulfamethoxazole or sulfadimidine; the initial concentration of the antibiotics in the antibiotic wastewater is less than or equal to 80 mg/L; the persulfate is peroxydisulfate or peroxymonosulfate.
10. The method for degrading antibiotics by using Fe-N self-doped algae-based carbon catalyst activated persulfate as claimed in claim 9, wherein the stirring time is 0.5 h-2 h; the time of the catalytic degradation reaction is 40 min-100 min.
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