CN114950521A - Mn-N-C site-containing algal-based carbon catalyst and preparation method and application thereof - Google Patents

Mn-N-C site-containing algal-based carbon catalyst and preparation method and application thereof Download PDF

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CN114950521A
CN114950521A CN202210379725.0A CN202210379725A CN114950521A CN 114950521 A CN114950521 A CN 114950521A CN 202210379725 A CN202210379725 A CN 202210379725A CN 114950521 A CN114950521 A CN 114950521A
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algae
manganese
site
carbon catalyst
algal
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CN114950521B (en
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周成赟
宋彪
夏雾
曾光明
何子翔
梁云涛
唐小峰
曾予希
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Hunan 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • 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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    • 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
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    • C02F2101/34—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • 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

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Abstract

The invention discloses an algal-based carbon catalyst containing Mn-N-C sites, and 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 of the manganese-containing carbon nitride and the algae-based biochar is subjected to ball milling and calcination to prepare the Mn-N-C site-containing algae-based carbon catalyst with multiple active sites and high catalytic activity, and the algae-based carbon catalyst can be used for efficiently degrading antibiotics in a water body when being used for activating persulfate, so that the antibiotics in the water body can be rapidly removed, and the method has the advantages of simple operation, high treatment efficiency, good removal effect, controllable environmental secondary pollution risk, wide environment adaptation range and the like, and has a good practical application prospect. 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

Mn-N-C site-containing algal-based carbon catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of environmental protection, and relates to an algal-based carbon catalyst containing Mn-N-C sites, and a preparation method and application thereof.
Background
A large amount of algae can be generated in the eutrophication process of lakes, and the fishing is the most direct and rapid way during the outbreak of the algae. However, the resource utilization of the harvested algae has been a major problem. At present, in the aspect of resource utilization, algae is mainly prepared into biomass energy by methods such as pyrolysis and the like, or is prepared into fertilizers and microorganism culture raw materials through biological fermentation, and bioactive substances can be extracted by utilizing an algae extraction technology. In order to better utilize resources, the algae can be carbonized into a carbon material, on one hand, the algae can be changed into useful resources, the harmless treatment of part of the algae is solved, on the other hand, the algae-based carbon is used as a catalyst to oxidize and degrade persistent organic pollutants in water, and the waste treatment 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 being used as a catalyst for activating persulfate, and is difficult to rapidly and thoroughly degrade organic pollution in water, thereby greatly limiting the wide application of the algae-based carbon material in the field of advanced oxidation. Therefore, the obtained algae-based carbon catalyst has multiple active sites and high catalytic activity, and 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 algal-based carbon catalyst with more active sites and high catalytic activity and a preparation method thereof, and also provides application of the Mn-N-C site-containing algal-based carbon catalyst in treatment of antibiotic wastewater.
In order to solve the technical problems, the invention adopts the following technical scheme.
A preparation method of an 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, and performing ball milling and calcination 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.
In the preparation method of the above-mentioned manganese-containing N-C site-containing algal-based carbon catalyst, the preparation method is further improved, and the preparation method of the manganese-containing carbon nitride comprises the following steps: mixing dicyanodiamine and 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 dicyanodiamine to manganese salt is 1: 0.01-0.08; the manganese salt is manganese chloride and/or manganese acetate.
In the preparation method of the above-mentioned Mn-N-C site-containing algae-based charcoal catalyst, the preparation method of the algae-based charcoal is further improved, and 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 h to obtain algae-based biochar; the algae-based biomass is at least one of freshwater spirulina, freshwater cyanobacteria and freshwater spirulina.
In the preparation method of the Mn-N-C site-containing algae-based carbon catalyst, the preparation method is further improved, and the preparation method of the Mn-N-C site-containing algae-based carbon catalyst comprises the following steps:
s1, mixing the manganese-containing carbon nitride and the algae-based biochar and carrying out ball milling;
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 site-containing algae-based carbon catalyst, the rotation speed of the ball milling is 300r/min to 350r/min in step S1; the ball milling time is 10 min-30 min.
In the preparation method of the above-mentioned catalyst containing Mn-N-C sites, further improvement is that in step S2, the calcination is performed in an inert atmosphere; the temperature rise rate of the calcination is 5-15 ℃/min; the calcining temperature is 700-900 ℃; the calcining time is 1-2 h.
As a general technical concept, the invention also provides an algal-based carbon catalyst containing Mn-N-C sites, which is prepared by the preparation method.
As a general technical concept, the invention also provides an application of the algae-based carbon catalyst containing Mn-N-C sites in treatment of antibiotic wastewater.
The application is further improved and comprises the following steps: mixing the Mn-N-C site-containing algae-based carbon catalyst with antibiotic wastewater, stirring, and adding persulfate to perform a catalytic degradation reaction to complete the degradation of the antibiotic in the wastewater.
In the application, the addition amount of the Mn-N-C site-containing algae-based carbon catalyst is further improved, and 0.1g of Mn-N-C site-containing algae-based carbon catalyst is added into each liter of antibiotic wastewater; the addition 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 antibiotic is enrofloxacin or ciprofloxacin; the initial concentration of the antibiotics in the antibiotic wastewater is 10 mg/L; the persulfate is a peroxydisulfate salt; the stirring time is 30 min; the time of the catalytic degradation reaction is 3 min-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, 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 monomolecular manner in the ball-milling process to form a host-guest structure; because the surface of the algae-based biochar contains rich nitrogen, manganese in manganese-containing carbon nitride can be better settled on the surface of the algae-based biochar, so that the intercalation of manganese atom level can be realized, the mixture after ball milling treatment is calcined, the algae-based biochar is further decomposed to form more stable graphitized carbon through high-temperature pyrolysis reaction in the inert gas atmosphere, and the pore structure still keeps the original porous structure to form an N-C structure; carbon in the manganese-containing carbon nitride partially disappears after high-temperature carbonization, Mn-N in the highly dispersed manganese-containing carbon nitride can be further converted into a Mn-N-C site-containing algae-based carbon catalyst by taking guest algae-based carbon as an N-C source, the Mn-N-C site-containing algae-based carbon catalyst has high dispersibility and is not agglomerated like other manganese-doped carbon catalysts, the catalytic performance can be better exerted, and finally manganese can be doped into a biological carbon net structure, and the Mn-N-C site-containing algae-based carbon catalyst with a plurality of 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 the manganese-containing carbon nitride to the algae-based biochar is optimized to be more than or equal to 0.3, particularly when the mass ratio of the manganese-containing carbon nitride to the algae-based biochar is 0.4-0.8, the quantity proportion relation of Mn sites, N sites and C sites in the catalyst is proper, and the catalytic activity of the catalyst is favorably and remarkably improved, because if the mass ratio is lower than 0.3 (such as when the mass ratio is 0.2), the manganese-containing carbon nitride accounts for a small amount, Mn-N-C active sites are contained in the catalyst in unit mass, and the Mn-N-C active sites are easily embedded by the algae-based biochar, so that the catalytic performance of the catalyst is reduced. When the mass ratio of the manganese-containing carbon nitride to the algae-based biochar exceeds 1, although Mn-N-C active sites can be increased, part of Mn can be agglomerated to form Mn clusters, so that the performance of the catalyst is greatly reduced, and therefore the ratio of the manganese-containing carbon nitride to the algae-based biochar is proper.
(3) The invention also provides the application of the Mn-N-C site-containing algae-based carbon catalyst in the treatment of antibiotic wastewater, the Mn-N-C site-containing algae-based carbon catalyst is used for activating persulfate to degrade antibiotics in a water body, the antibiotics can be rapidly removed, and the method has the advantages of simple operation, high treatment efficiency, good removal effect, controllable secondary environmental pollution risk, wide environment adaptation 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 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 one another 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 shows an algal based charcoal catalyst containing Mn-N-C sites (Mn) prepared in example 1 of the present invention SA -CN/BC-2).
FIG. 2 is an algal based charcoal containing Mn-N-C sites obtained in example 1 of the present inventionCatalyst (Mn) SA TEM image of-CN/BC-2), wherein (a) is TEM image and (b) is EDS image.
FIG. 3 shows an algal based charcoal catalyst containing Mn-N-C sites (Mn) according to example 2 of the present invention SA -CN/BC-1，Mn SA -CN/BC-2，Mn SA -CN/BC-3) and an algal charcoal catalyst (Mn) PA -CN/BC) on the degradation effect of enrofloxacin in the water body.
FIG. 4 shows an algal based charcoal catalyst containing Mn-N-C sites (Mn) according to 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), and algae-based carbon catalyst (Mn) PA -CN/BC) on the degradation effect of enrofloxacin in the water body.
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 instruments used in the following examples are commercially available.
Example 1
The preparation method of the Mn-N-C site-containing algae-based carbon catalyst is prepared by using dicyanodiamine, manganese salt and algae-based biomass as raw materials and assisting mechanical ball milling through calcination, and comprises the following steps:
(1) preparation of manganese-containing polymeric carbon nitride: 10g of dicyanodiamine and 0.4g of manganese chloride are mixed and ground, the temperature is raised to 550 ℃ at the speed of 3 ℃/min and is kept for 2h for calcination, and the manganese-containing polymeric carbon nitride (Mn-PCN) is obtained.
(2) Preparing the algae-based biochar: taking 10g of spirulina, adding into N 2 Heating to 500 ℃ at the speed of 10 ℃/min in the atmosphere, and keeping for 2h for calcination to obtain the algae-based Biochar (BC).
(3) Preparing an algal-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 1: 0.2, 1: 0.5 and 1: 1, placing the mixture in an agate pot (20 balls in the agate pot and 80 small balls) of a ball mill, carrying out ball milling under the condition that the rotating speed is 250r/min, rotating positively and negatively every five minutes, and totally rotating once per five minutesMechanically ball-milling for 30min, transferring the mixture obtained after ball-milling into a tube furnace, and performing ball milling in N 2 Under protection, heating to 700 ℃ at the speed of 7 ℃/min and keeping the temperature 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 is 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, and the Mn-N-C site-containing algae-based carbon catalyst is named as Mn SA -CN/BC-1，Mn SA -CN/BC-2，Mn SA -CN/BC-3。
In the embodiment, the influence of different ball milling rotating speeds and different ball milling times on the performance of the Mn-N-C site-containing algae-based carbon catalyst is also considered, and specifically:
mixing the algae-based biochar and the manganese-containing polymeric carbon nitride according to the mass ratio of 1: 0.5, placing the obtained mixture into an agate pot (20 balls in the agate pot and 80 small balls) of a ball mill, performing ball milling under the conditions of the rotating speed of 200r/min and 300r/min respectively, performing positive and negative rotation once every five minutes for 30min in total, then transferring the mixture obtained after ball milling into a tubular furnace, and performing ball milling in an N-N (nitrogen-nitrogen) furnace 2 Under protection, heating to 700 ℃ at the speed of 7 ℃/min and keeping the temperature 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 the rotation speed of 200r/min and 300r/min is named as Mn in sequence 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 1: 0.5, placing the obtained mixture into an agate pot (20 balls in the agate pot and 80 small balls) of a ball mill, carrying out ball milling under the condition of the rotating speed of 250r/min, carrying out positive and negative rotation once every five minutes for respectively carrying out ball milling for 10min and 60min, transferring the mixture obtained after ball milling into a tubular furnace, and carrying out ball milling in a N-tube furnace 2 Under protection, heating to 700 ℃ at the speed of 7 ℃/min and keeping the temperature 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 named as Mn in sequence SA -CN/BC-6，Mn SA -CN/BC-7。
FIG. 1 shows an algal based charcoal catalyst containing Mn-N-C sites (Mn) prepared in example 1 of the present invention SA -CN/BC-2).
FIG. 2 shows an algal based charcoal catalyst containing Mn-N-C sites (Mn) prepared in example 1 of the present invention SA -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 algal-based carbon catalyst was successful, and the distribution of Mn in the algal-based carbon was found to be relatively uniform from both the energy spectrum and the XPS results.
Comparative example 1:
the algae-based carbon catalyst is prepared by calcining dicyanodiamide, manganese salt and algae-based biomass serving as raw materials and comprises the following steps: the algal-based biochar prepared in example 1 and manganese-containing polymeric carbon nitride were mixed at a mass ratio of 1: 0.5, and the resulting mixture was transferred to a tube furnace and heated in N 2 Under protection, heating to 700 ℃ at the speed of 7 ℃/min and keeping for 70min for calcination to obtain the algae-based carbon catalyst named as Mn PA -CN/BC。
Example 2
An application of Mn-N-C site-containing algae-based carbon catalyst in treating antibiotic wastewater, in particular to an application of Mn-N-C site-containing algae-based carbon catalyst as a catalyst for activating peroxydisulfate to degrade enrofloxacin in a water body, which comprises the following steps:
the algal-based charcoal catalyst containing Mn-N-C sites (Mn) prepared 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 Biochar (BC), and the algal biochar catalyst (Mn) prepared in comparative example 1 PA -CN/BC), 5mg of each, respectively placing the mixture into 50mL of enrofloxacin solution with the concentration of 10mg/L, stirring the mixture for 30 minutes to reach adsorption balance, and then adding 0.1mL of Peroxydisulfate (PMS) solution with the concentration of 0.5M to perform catalytic degradation reaction to complete the degradation of enrofloxacin in the water body.
In the catalytic reaction process, 1mL of enrofloxacin solution is taken at regular intervals, 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 charcoal catalyst containing Mn-N-C sites (Mn) according to example 2 of the present invention SA -CN/BC-1，Mn SA -CN/BC-2，Mn SA -CN/BC-3) and an algal charcoal catalyst (Mn) PA -CN/BC) on the degradation effect of enrofloxacin in the water body. As can be seen from FIG. 3, the catalyst was compared with the algal based charcoal catalyst (Mn) PA -CN/BC), the Mn-N-C site-containing algae-based carbon catalyst prepared by ball milling and calcining in the invention can effectively activate peroxydisulfate, thereby effectively degrading enrofloxacin in water, and particularly, the Mn-N-C site-containing algae-based carbon catalyst (Mn) prepared when the mass ratio of algae-based biochar to manganese-containing polymeric carbon nitride is 1: 0.5 SA the-CN/BC-2) can degrade the enrofloxacin within 5 minutes, and has good application value and application prospect.
FIG. 4 shows an algal based charcoal catalyst containing Mn-N-C sites (Mn) according to 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), and algae-based carbon catalyst (Mn) PA -CN/BC) on the degradation effect of enrofloxacin in the water body. As can be seen from FIG. 4, the Mn-N-C site-containing algal 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 the water body, and the longer the ball milling time is, the better the catalytic performance of the algae-based carbon catalytic base is improved under the same ball milling speed.
From the above results, it can be 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 subjected to ball milling and calcination to prepare the Mn-N-C site-containing algae-based carbon catalyst with many active sites and high catalytic activity, and the Mn-N-C site-containing algae-based carbon catalyst can be used as a catalyst for efficiently degrading antibiotics in water when being used for activating persulfate, so that the antibiotics in the water can be rapidly removed. In addition, the method utilizes the algae-based carbon catalyst containing Mn-N-C sites to treat 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.
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 modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention.

Claims (10)

1. A preparation method of an 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 more than 0.2.
2. The method for preparing an algal-based carbon catalyst containing Mn-N-C sites according to claim 1, wherein the mass ratio of the manganese-containing carbon nitride to the algal-based biochar is not less than 0.3.
3. The method for preparing an algal-based carbon catalyst containing Mn-N-C sites according to claim 2, wherein the mass ratio of the manganese-containing carbon nitride to the algal-based biochar is 0.4-0.8.
4. The method for preparing an Mn-N-C site-containing algal-based carbon catalyst according to claim 3, wherein the method for preparing manganese-containing carbon nitride comprises the steps of: mixing dicyanodiamine and 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 dicyanodiamine 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 h to obtain algae-based biochar; the algae-based biomass is at least one of freshwater spirulina, freshwater cyanobacteria and freshwater spirulina.
5. The method for preparing Mn-N-C site-containing algal-based carbon catalyst according to any one of claims 1 to 4, wherein the method for preparing Mn-N-C site-containing algal-based carbon catalyst comprises the following steps:
s1, mixing the manganese-containing carbon nitride and the algae-based biochar and carrying out ball milling;
s2, calcining the mixture obtained after ball milling in the step S1 to obtain the Mn-N-C site-containing algae-based carbon catalyst.
6. The method for preparing an Mn-N-C site-containing algal-based carbon catalyst as claimed in claim 5, wherein in step S1, the rotation speed of the ball mill is 300r/min to 350 r/min; the ball milling time is 10 min-30 min;
in step S2, the calcination is performed under an inert atmosphere; the temperature rise rate of the calcination is 5-15 ℃/min; the calcining temperature is 700-900 ℃; the calcining time is 1-2 h.
7. An algal-based carbon catalyst containing Mn-N-C sites, which is characterized by being prepared by the preparation method of any one of claims 1 to 6.
8. Use of the Mn-N-C site-containing algal-based charcoal catalyst according to claim 7 for treating antibiotic wastewater.
9. Use according to claim 8, characterized in that it comprises the following steps: mixing the Mn-N-C site-containing algae-based carbon catalyst with antibiotic wastewater, stirring, and adding persulfate to perform a catalytic degradation reaction to complete the degradation of the antibiotic in the wastewater.
10. The use of claim 9, wherein the addition amount of the Mn-N-C site-containing algal-based carbon catalyst is 0.1g per liter of antibiotic wastewater added with the Mn-N-C site-containing algal-based carbon catalyst; the addition 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 antibiotic is enrofloxacin or ciprofloxacin; the initial concentration of the antibiotics in the antibiotic wastewater is 10 mg/L; the persulfate is a peroxydisulfate salt; the stirring time is 30 min; the time of the catalytic degradation reaction is 3 min-5 min.
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