CN114950521B - Mn-N-C site-containing algae-based carbon catalyst and preparation method and application thereof - Google Patents
Mn-N-C site-containing algae-based carbon catalyst and preparation method and application thereof Download PDFInfo
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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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- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
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- 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
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/38—Organic compounds containing nitrogen
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
Abstract
The invention discloses an algae-based carbon catalyst containing Mn-N-C sites, a preparation method and application thereof. According to the invention, manganese-containing carbon nitride and algae-based biochar are used as raw materials, and the mixture is subjected to ball milling and calcination to obtain the Mn-N-C site-containing algae-based carbon catalyst with multiple active sites and high catalytic activity. Meanwhile, the preparation method provided by the invention has the advantages of simple process, convenience in operation, high preparation efficiency and the like, is suitable for large-scale preparation, and is beneficial to industrial application.
Description
Technical Field
The invention belongs to the technical field of environmental protection, and relates to an algae-based carbon catalyst containing Mn-N-C sites, and a preparation method and application thereof.
Background
During the eutrophication of lakes, a lot of algae are produced, and during the algae burst, salvaging is the most direct and quick way. However, the recycling of the algae obtained by salvaging is always a big problem. At present, algae are mainly prepared into biomass energy sources by methods such as pyrolysis, or are prepared into fertilizers and microorganism culture raw materials by biological fermentation, and bioactive substances can be extracted by utilizing an algae extraction technology. In order to better utilize resources, algae can be carbonized into carbon materials, on one hand, the algae can be changed into useful resources, the harmless treatment of partial algae is solved, and on the other hand, the algae-based carbon is used as a catalyst to oxidatively degrade persistent organic pollutants in water, so that the treatment of waste by waste is realized. However, the existing algae-based carbon material still has the defects of few active sites, low catalytic activity and the like, so that the existing algae-based carbon material is difficult to effectively activate persulfate when used as a catalyst for activating persulfate, and thus organic pollution in water is difficult to degrade rapidly and thoroughly, and the wide application of the algae-based carbon material in the advanced oxidation field is greatly limited. Therefore, the obtained algae-based carbon catalyst with multiple active sites and high catalytic activity has important significance for efficiently degrading organic pollutants (such as antibiotics) in water.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides an Mn-N-C site-containing algae-based carbon catalyst with multiple active sites and high catalytic activity and a preparation method thereof, and also provides application of the Mn-N-C site-containing algae-based carbon catalyst in treating antibiotic wastewater.
In order to solve the technical problems, the invention adopts the following technical scheme.
The preparation method of the Mn-N-C site-containing algae-based carbon catalyst comprises the steps of taking manganese-containing carbon nitride and algae-based biochar as raw materials, ball milling and calcining to obtain the Mn-N-C site-containing algae-based carbon catalyst; the mass ratio of the manganese-containing carbon nitride to the algae-based biochar is greater than 0.2.
The preparation method of the Mn-N-C site-containing algae-based carbon catalyst is further improved, and the mass ratio of the manganese-containing carbon nitride to the algae-based biochar is more than or equal to 0.3.
The preparation method of the Mn-N-C site-containing algae-based carbon catalyst is further improved, and the mass ratio of the manganese-containing carbon nitride to the algae-based biochar is 0.4-0.8.
The preparation method of the Mn-N-C site-containing algae-based carbon catalyst is further improved, and the preparation method of the Mn-containing carbon nitride comprises the following steps of: mixing dicyandiamide with manganese salt, heating to 450-550 ℃ according to the heating rate of 3-5 ℃/min, and calcining for 1-2 h to obtain manganese-containing carbon nitride; the mass ratio of dicyandiamide to manganese salt is 1:0.01-0.08; the manganese salt is manganese chloride and/or manganese acetate.
The preparation method of the Mn-N-C site-containing algae-based carbon catalyst is further improved, and the preparation method of the algae-based biochar comprises the following steps of: heating the algae-based biomass to 400-520 ℃ according to the heating rate of 3-5 ℃/min, and calcining for 1-2 h to obtain the algae-based biochar; the algae-based biomass is at least one of freshwater spirulina, freshwater cyanobacteria and freshwater silk algae.
The preparation method of the Mn-N-C site-containing algae-based carbon catalyst is further improved, and the preparation method of the Mn-N-C site-containing algae-based carbon catalyst comprises the following steps of:
s1, mixing manganese-containing carbon nitride and algae-based biochar, and performing ball milling;
and S2, calcining the mixture obtained after ball milling in the step S1 to obtain the Mn-N-C site-containing algae-based carbon catalyst.
In the preparation method of the Mn-N-C locus containing algae-based carbon catalyst, which is further improved, in the step S1, the rotation speed of ball milling is 300 r/min-350 r/min; the ball milling time is 10 min-30 min.
In the preparation method of the Mn-N-C site-containing algae-based carbon catalyst, which is further improved, in the step S2, the calcination is performed under an inert atmosphere; the temperature rising rate of the calcination is 5-15 ℃/min; the calcining temperature is 700-900 ℃; the calcination time is 1-2 h.
As a general technical concept, the invention also provides an algae-based carbon catalyst containing Mn-N-C sites, which is prepared by the preparation method.
As a general technical concept, the invention also provides application of the Mn-N-C site-containing algae-based carbon catalyst in treating antibiotic wastewater.
The above application, further improved, comprising the steps of: mixing an algae-based carbon catalyst containing Mn-N-C sites with the antibiotic wastewater, stirring, adding persulfate to perform catalytic degradation reaction, and finishing degradation of the antibiotic in the wastewater.
The application is further improved, wherein the addition amount of the Mn-N-C site-containing algae-based carbon catalyst is 0.1g of Mn-N-C site-containing algae-based carbon catalyst added into each liter of antibiotic wastewater; the adding amount of the persulfate is 1mmol of persulfate added into each liter of antibiotic wastewater; the antibiotics in the antibiotic wastewater are quinolone antibiotics; the quinolone antibiotics are enrofloxacin or ciprofloxacin; the initial concentration of antibiotics in the antibiotic wastewater is 10mg/L; the persulfate is peroxodisulfate; the stirring time is 30min; the time of the catalytic degradation reaction is 3-5 min.
Compared with the prior art, the invention has the advantages that:
(1) Aiming at the defects of few active sites, low catalytic activity and the like of the existing algae-based carbon material, the invention creatively provides a preparation method of an algae-based carbon catalyst containing Mn-N-C sites, which takes manganese-containing carbon nitride and algae-based biochar as raw materials, and prepares the algae-based carbon catalyst containing Mn-N-C sites after ball milling and calcining the mixture of the manganese-containing carbon nitride and the algae-based biochar, wherein the mass ratio of the manganese-containing carbon nitride to the algae-based biochar is more than 0.2. In the invention, firstly, the mixture of manganese-containing carbon nitride and algae-based biochar is ball-milled, and the manganese-containing carbon nitride can be wrapped on the surface of the algae-based biochar in a highly dispersed single-molecule form in the ball milling process to form a host-guest structure; as the surface of the algae-based biochar contains rich nitrogen, manganese in the manganese-containing carbon nitride can be better Mou Ding on the surface of the algae-based biochar, thereby realizing intercalation of manganese atom level, further calcining the mixture after ball milling treatment, and further decomposing the algae-based biochar to form more stable graphitized carbon through thermal pyrolysis reaction in inert gas atmosphere, wherein the pore channel structure still keeps the original porous structure to form an N-C structure; the carbon in the manganese-containing carbon nitride is partially disappeared through high-temperature carbonization, the Mn-N in the highly dispersed manganese-containing carbon nitride can be further converted into an Mn-N-C site-containing algae-based carbon catalyst by taking the guest algae-based carbon as an N-C source, and the Mn-N-C site-containing algae-based carbon catalyst has high dispersibility, is not agglomerated like other manganese-doped carbon catalysts, can better exert catalytic performance, and can finally dope manganese into a biological carbon net structure, so that the Mn-N-C site-containing algae-based carbon catalyst with more active sites and high catalytic activity is prepared. Meanwhile, the preparation method provided by the invention has the advantages of simple process, convenience in operation, high preparation efficiency and the like, is suitable for large-scale preparation, and is beneficial to industrial application.
(2) According to the preparation method, the mass ratio of manganese-containing carbon nitride to algae-based biochar is optimized to be more than or equal to 0.3, and particularly when the mass ratio of manganese-containing carbon nitride to algae-based biochar is 0.4-0.8, the number proportion relationship of Mn sites, N sites and C sites in the catalyst is proper, so that the catalyst activity of the catalyst is more beneficial to be remarkably improved, and the manganese-containing carbon nitride accounts for less than 0.3 (when the mass ratio is 0.2) because the Mn-N-C active sites in the catalyst in unit mass are less, and the algae-based biochar is easy to embed the Mn-N-C active sites, so that the catalyst performance is reduced. When the mass ratio of the manganese-containing carbon nitride to the algae-based carbon is more than 1, the Mn-N-C active sites may be increased, but a part of Mn may be agglomerated to form Mn clusters, which may greatly deteriorate the performance of the catalyst, so that the ratio of the manganese-containing carbon nitride to the algae-based carbon is proper.
(3) The invention also provides application of the Mn-N-C site-containing algae-based carbon catalyst in treating antibiotic wastewater, and the Mn-N-C site-containing algae-based carbon catalyst is utilized to activate persulfate to degrade antibiotics in water, so that the quick removal of the antibiotics can be realized, and the method has the advantages of simplicity in operation, high treatment efficiency, good removal effect, controllable risk of secondary environmental pollution, wide application environment range and the like, and has good practical application prospect. According to the invention, the algae-based carbon catalyst containing Mn-N-C sites is used for treating antibiotic wastewater, and on one hand, the algae organic matters are recycled, so that the treatment pressure of near-coastal eutrophication is reduced, and the environmental treatment cost is reduced; on the other hand, a way is provided for degrading antibiotics in the actual water body, and the treatment of wastes with the wastes is truly realized.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
FIG. 1 shows an Mn-N-C site-containing algal-based carbon catalyst (Mn) prepared in example 1 of the present invention SA -XPS map of CN/BC-2).
FIG. 2 shows an Mn-N-C site-containing algal-based carbon catalyst (Mn) prepared in example 1 of the present invention SA -a TEM image of CN/BC-2), wherein (a) is a TEM image and (b) is an EDS image.
FIG. 3 shows an algal-based carbon catalyst (Mn) containing Mn-N-C sites in example 2 of the present invention SA -CN/BC-1，Mn SA -CN/BC-2，Mn SA -CN/BC-3) and an algae-based carbon catalyst (Mn PA -CN/BC) degradation effect pattern of enrofloxacin in water.
FIG. 4 shows an algal-based carbon catalyst (Mn) containing Mn-N-C sites in example 2 of the present invention SA -CN/BC-4，Mn SA -CN/BC-5，Mn SA -CN/BC-6，Mn SA -CN/BC-7), manganese-containing polymeric carbon nitride (Mn-PCN), algae-based Biochar (BC), algae-based carbon catalyst (Mn PA -CN/BC) degradation effect pattern of enrofloxacin in water.
Detailed Description
The invention is further described below in connection with the drawings and the specific preferred embodiments, but the scope of protection of the invention is not limited thereby. The materials and instruments used in the examples below are all commercially available.
Example 1
The preparation method of the Mn-N-C site-containing algae-based carbon catalyst is characterized in that dicyandiamide, manganese salt and algae-based biomass are used as raw materials, and the materials are prepared by mechanical ball milling and calcining, and comprises the following steps:
(1) Preparing manganese-containing polymeric carbon nitride: 10g of dicyandiamide and 0.4g of manganese chloride are mixed and ground, the temperature is raised to 550 ℃ at the speed of 3 ℃/min, and the mixture is kept for 2 hours for calcination, thus obtaining manganese-containing polymeric carbon nitride (Mn-PCN).
(2) Preparing algae-based biochar: taking 10g of spirulina, adding into N 2 And (3) heating to 500 ℃ at a speed of 10 ℃/min under the atmosphere, and keeping for 2 hours for calcination to obtain the algae-based Biochar (BC).
(3) Preparing an algae-based carbon catalyst containing Mn-N-C sites: mixing the algae-based biochar and the manganese-containing polymeric carbon nitride according to the mass ratio of the algae-based biochar to the manganese-containing polymeric carbon nitride of 1:0.2, 1:0.5 and 1:1, placing the obtained mixture into an agate tank (20 middle balls and 80 small balls in the agate tank) of a ball mill, performing ball milling at the rotating speed of 250r/min, performing forward and reverse rotation every five minutes for 30min, transferring the mixture obtained after ball milling into a tube furnace, and performing ball milling on N 2 Under protection, heating to 700 ℃ at a speed of 7 ℃/min and maintaining for 70min for calcination to obtain the Mn-N-C site-containing algae-based carbon catalyst, wherein the Mn-N-C site-containing algae-based carbon catalyst prepared when the mass ratio of the algae-based biochar to the manganese-containing polymeric carbon nitride is 1:0.2, 1:0.5 and 1:1 is named Mn in turn SA -CN/BC-1，Mn SA -CN/BC-2，Mn SA -CN/BC-3。
In the embodiment, the influence of different ball milling speeds and different ball milling times on the performance of the Mn-N-C locus containing algae-based carbon catalyst is also examined, and the method specifically comprises the following steps:
mixing the algae-based biochar and the manganese-containing polymeric carbon nitride according to the mass ratio of the algae-based biochar to the manganese-containing polymeric carbon nitride of 1:0.5, placing the obtained mixture into an agate tank (20 middle balls and 80 small balls in the agate tank) of a ball mill, respectively performing ball milling at the rotating speeds of 200r/min and 300r/min, performing forward and reverse rotation every five minutes for 30min, then transferring the mixture obtained after ball milling into a tubular furnace, and performing N-phase ball milling on the mixture 2 Under protection, heating to 700 ℃ at a speed of 7 ℃/min and maintaining for 70min for calcination to obtain the Mn-N-C site-containing algae-based carbon catalyst, wherein the Mn-N-C site-containing algae-based carbon catalyst prepared under the conditions of 200r/min and 300r/min rotating speed is sequentially named Mn SA -CN/BC-4，Mn SA -CN/BC-5。
Mixing the algae-based biochar and the manganese-containing polymeric carbon nitride according to the mass ratio of the algae-based biochar to the manganese-containing polymeric carbon nitride of 1:0.5, placing the obtained mixture into an agate tank (20 balls in the agate tank and 80 balls in the agate tank), performing ball milling under the condition of the rotating speed of 250r/min, performing forward and reverse rotation every five minutes for 10min and 60min respectively, then transferring the mixture obtained after ball milling into a tubular furnace, and performing N-type ball milling on the mixture 2 Under protection, heating to 700 ℃ at a speed of 7 ℃/min and keeping for 70min for calcination to obtain the Mn-N-C site-containing algae-based carbon catalyst, wherein the Mn-N-C site-containing algae-based carbon catalyst prepared under the conditions of ball milling time of 10min and 60min is sequentially named as Mn SA -CN/BC-6，Mn SA -CN/BC-7。
FIG. 1 shows an Mn-N-C site-containing algal-based carbon catalyst (Mn) prepared in example 1 of the present invention SA -XPS map of CN/BC-2).
FIG. 2 shows an Mn-N-C site-containing algal-based carbon catalyst (Mn) prepared in example 1 of the present invention SA -a TEM image of CN/BC-2), wherein (a) is a TEM image and (b) is an EDS image.
As can be seen from FIGS. 1 and 2, the preparation of the Mn-N-C site-containing algae-based carbon catalyst was successful, and the distribution of Mn in the algae-based carbon was found to be relatively uniform from both the energy spectrum and the XPS result.
Comparative example 1:
algae-basedThe carbon catalyst is prepared by taking dicyandiamide, manganese salt and algae-based biomass as raw materials through calcination, and comprises the following steps: mixing the algae-based biochar and manganese-containing polymeric carbon nitride prepared in example 1 at a mass ratio of 1:0.5, transferring the obtained mixture into a tube furnace, and adding N 2 Under protection, the temperature is raised to 700 ℃ at the speed of 7 ℃/min and kept for 70min for calcination, and the algae-based carbon catalyst named Mn is obtained PA -CN/BC。
Example 2
An application of an Mn-N-C site-containing algae-based carbon catalyst in treating antibiotic wastewater, in particular to an application of an Mn-N-C site-containing algae-based carbon catalyst as a catalyst in activating peroxodisulfate to degrade enrofloxacin in water, comprising the following steps:
the Mn-N-C site-containing algal-based carbon catalyst (Mn) obtained in example 1 was taken SA -CN/BC-1，Mn SA -CN/BC-2，Mn SA -CN/BC-3，Mn SA -CN/BC-4，Mn SA -CN/BC-5，Mn SA -CN/BC-6，Mn SA -CN/BC-7), manganese-containing polymeric carbon nitride (Mn-PCN), algal-based Biochar (BC) and algal-based carbon catalyst (Mn) obtained in comparative example 1 PA -CN/BC), 5mg each, are respectively placed in 50mL of enrofloxacin solution with the concentration of 10mg/L, stirred for 30 minutes to reach adsorption equilibrium, and then 0.1mL of Peroxodisulfate (PMS) solution with the concentration of 0.5M is added for catalytic degradation reaction, so as to complete the degradation of enrofloxacin in the water body.
In the catalytic reaction process, 1mL of enrofloxacin solution is taken at regular intervals, the solution is filtered by a 0.22 mu M membrane filter, the reaction is stopped by 20 mu L of 0.1M sodium thiosulfate solution, the concentration of enrofloxacin in the solution is measured by high performance liquid chromatography, and the degradation efficiency of different catalysts on enrofloxacin under different time conditions is calculated.
FIG. 3 shows an algal-based carbon catalyst (Mn) containing Mn-N-C sites in example 2 of the present invention SA -CN/BC-1，Mn SA -CN/BC-2，Mn SA -CN/BC-3) and an algae-based carbon catalyst (Mn PA -CN/BC) degradation effect pattern of enrofloxacin in water. As can be seen from fig. 3, compared with the algae-based carbon catalyst (Mn PA -CN/BC), in the present invention, is obtained by ball milling and calciningThe Mn-N-C site-containing algae-based carbon catalyst of (3) can effectively activate peroxodisulfate, thereby effectively degrading enrofloxacin in water, in particular, when the mass ratio of the algae-based biochar to the Mn-containing polymeric carbon nitride is 1:0.5 (Mn SA CN/BC-2) can degrade enrofloxacin within 5 minutes, and has good application value and application prospect.
FIG. 4 shows an algal-based carbon catalyst (Mn) containing Mn-N-C sites in example 2 of the present invention SA -CN/BC-4，Mn SA -CN/BC-5，Mn SA -CN/BC-6，Mn SA -CN/BC-7), manganese-containing polymeric carbon nitride (Mn-PCN), algae-based Biochar (BC), algae-based carbon catalyst (Mn PA -CN/BC) degradation effect pattern of enrofloxacin in water. As can be seen from FIG. 4, the Mn-N-C site-containing algae-based carbon catalyst (Mn) prepared under the conditions of different ball milling speeds and different ball milling times in the present invention SA -CN/BC-4，Mn SA -CN/BC-5，Mn SA -CN/BC-6，Mn SA CN/BC-7) can effectively degrade enrofloxacin in water, and the longer the ball milling time is, the more favorable the catalytic performance of the algae-based carbon catalytic base is improved.
From the above results, it is known that in the invention, manganese-containing carbon nitride and algae-based biochar are used as raw materials, and the mixture of the manganese-containing carbon nitride and the algae-based biochar is ball-milled and calcined to prepare the Mn-N-C site-containing algae-based carbon catalyst with multiple active sites and high catalytic activity, and the Mn-N-C site-containing algae-based carbon catalyst can efficiently degrade antibiotics in water when being used as a catalyst for activating persulfate, thereby realizing rapid removal of the antibiotics in the water. In addition, in the invention, the algae-based carbon catalyst containing Mn-N-C sites is used for treating the antibiotic wastewater, and on one hand, the resource utilization of algae organisms is realized, thereby being beneficial to reducing the treatment pressure of near-coastal eutrophication and reducing the environmental treatment cost; on the other hand, a way is provided for degrading antibiotics in the actual water body, and the treatment of wastes with the wastes is truly realized.
The above description is only of the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. While the invention has been described in terms of preferred embodiments, it is not intended to be limiting. Any person skilled in the art can make many possible variations and modifications to the technical solution of the present invention or equivalent embodiments using the method and technical solution disclosed above without departing from the spirit and technical solution of the present invention. Therefore, any simple modification, equivalent substitution, equivalent variation and modification of the above embodiments according to the technical substance of the present invention, which do not depart from the technical solution of the present invention, still fall within the scope of the technical solution of the present invention.
Claims (9)
1. The preparation method of the Mn-N-C site-containing algae-based carbon catalyst is characterized in that manganese-containing carbon nitride and algae-based biochar are used as raw materials, and the Mn-N-C site-containing algae-based carbon catalyst is prepared by ball milling and calcining; the mass ratio of the manganese-containing carbon nitride to the algae-based biochar is 0.4-0.8; the rotation speed of the ball milling is 300 r/min-350 r/min; the ball milling time is 30min; the preparation method of the manganese-containing carbon nitride comprises the following steps: and mixing dicyandiamide with manganese salt, heating to 450-550 ℃ according to the heating rate of 3-5 ℃/min, and calcining for 1 h-2 h to obtain manganese-containing carbon nitride.
2. The method for preparing an Mn-N-C site-containing algae-based carbon catalyst according to claim 1, wherein the mass ratio of dicyandiamide to manganese salt is 1:0.01-0.08; the manganese salt is manganese chloride and/or manganese acetate;
the preparation method of the algae-based biochar comprises the following steps: heating the algae-based biomass to 400-520 ℃ according to the heating rate of 3-5 ℃/min, and calcining for 1-2 hours h to obtain the algae-based biochar; the algae-based biomass is at least one of freshwater spirulina, freshwater cyanobacteria and freshwater silk algae.
3. The method for preparing an Mn-N-C site-containing algal-based carbon catalyst according to claim 1 or 2, wherein the method for preparing an Mn-N-C site-containing algal-based carbon catalyst comprises the steps of:
s1, mixing manganese-containing carbon nitride and algae-based biochar, and performing ball milling;
and S2, calcining the mixture obtained after ball milling in the step S1 to obtain the Mn-N-C site-containing algae-based carbon catalyst.
4. The method for preparing an Mn-N-C site-containing algal-based carbon catalyst according to claim 3, wherein in the step S2, the calcination is performed under an inert atmosphere; the temperature rising rate of the calcination is 5-15 ℃/min; the calcining temperature is 700-900 ℃; the calcination time is 1-2 h.
5. An Mn-N-C site-containing algal-based carbon catalyst, characterized by being prepared by the preparation method according to any one of claims 1 to 4.
6. Use of the Mn-N-C site containing algae-based carbon catalyst of claim 5 in the treatment of antibiotic wastewater.
7. The use according to claim 6, characterized by the steps of: mixing an algae-based carbon catalyst containing Mn-N-C sites with the antibiotic wastewater, stirring, adding persulfate to perform catalytic degradation reaction, and finishing degradation of the antibiotic in the wastewater.
8. The use according to claim 7, wherein the addition amount of the Mn-N-C site-containing algae-based carbon catalyst is 0.1 g/liter of antibiotic wastewater; the adding amount of the persulfate is 1mmol of persulfate added into each liter of antibiotic wastewater; the antibiotics in the antibiotic wastewater are quinolone antibiotics; the initial concentration of the antibiotics in the antibiotic wastewater is 10mg/L; the persulfate is peroxodisulfate; the stirring time is 30min; the time of the catalytic degradation reaction is 3-5 min.
9. The use according to claim 8, wherein the quinolone antibiotic is enrofloxacin or ciprofloxacin.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108380233A (en) * | 2018-03-07 | 2018-08-10 | 湖南大学 | Phosphorus doping carbonitride/carbonitride homotype heterojunction photocatalyst and its preparation method and application |
| CN109731605A (en) * | 2019-02-28 | 2019-05-10 | 哈尔滨工业大学 | A kind of metal composite situ Nitrogen Doping carbon microspherical catalyst and its application |
| CN109908936A (en) * | 2019-03-14 | 2019-06-21 | 浙江师范大学 | A kind of monatomic load carbon nitride catalyst of visible light-responded manganese and its preparation method and application |
| CN110400939A (en) * | 2019-08-12 | 2019-11-01 | 四川轻化工大学 | A kind of preparation method of biomass nitrating porous carbon oxygen reduction catalyst |
| CN111013632A (en) * | 2019-12-25 | 2020-04-17 | 上海电力大学 | Catalyst for degrading rhodamine B and preparation and application thereof |
| CN112516964A (en) * | 2020-11-16 | 2021-03-19 | 湖南大学 | Nitrogen-doped biochar and preparation method and application thereof |
| WO2022021506A1 (en) * | 2020-07-30 | 2022-02-03 | 大连工业大学 | Preparation of ultrathin porous carbon nitride nano-photocatalyst and applications thereof in photocatalytically oxidizing fructose to synthesize lactic acid |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108380233A (en) * | 2018-03-07 | 2018-08-10 | 湖南大学 | Phosphorus doping carbonitride/carbonitride homotype heterojunction photocatalyst and its preparation method and application |
| CN109731605A (en) * | 2019-02-28 | 2019-05-10 | 哈尔滨工业大学 | A kind of metal composite situ Nitrogen Doping carbon microspherical catalyst and its application |
| CN109908936A (en) * | 2019-03-14 | 2019-06-21 | 浙江师范大学 | A kind of monatomic load carbon nitride catalyst of visible light-responded manganese and its preparation method and application |
| CN110400939A (en) * | 2019-08-12 | 2019-11-01 | 四川轻化工大学 | A kind of preparation method of biomass nitrating porous carbon oxygen reduction catalyst |
| CN111013632A (en) * | 2019-12-25 | 2020-04-17 | 上海电力大学 | Catalyst for degrading rhodamine B and preparation and application thereof |
| WO2022021506A1 (en) * | 2020-07-30 | 2022-02-03 | 大连工业大学 | Preparation of ultrathin porous carbon nitride nano-photocatalyst and applications thereof in photocatalytically oxidizing fructose to synthesize lactic acid |
| CN112516964A (en) * | 2020-11-16 | 2021-03-19 | 湖南大学 | Nitrogen-doped biochar and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Chao He等.Rational design to manganese and oxygen co-doped polymeric carbon nitride for efficient nonradical activation of peroxymonosulfate and the mechanism insight.《Chemical EngineeringJournal》.2021,全文第1-11页. * |
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