CN114570402A - Preparation method of carbon-defect-containing and oxygen-doped carbon nitride photocatalytic material and application of carbon-defect-containing and oxygen-doped carbon nitride photocatalytic material in removal of tetracycline in water body - Google Patents
Preparation method of carbon-defect-containing and oxygen-doped carbon nitride photocatalytic material and application of carbon-defect-containing and oxygen-doped carbon nitride photocatalytic material in removal of tetracycline in water body Download PDFInfo
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- 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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a preparation method of a carbon defect and oxygen doped carbon nitride photocatalytic material and application of the material in removing tetracycline antibiotics in a water body, which is characterized in that commercial urea crystals are ground into uniform fine particles, then the particles are sealed in an alumina crucible, and pure-phase Carbon Nitride (CN) is prepared by temperature programming from room temperature to 550 ℃ and keeping the temperature for 3 hours at constant temperature in a quartz tube furnace; finally, the pure-phase carbon nitride is respectively kept for certain time (4, 6, 8 and 10 hours) at 180 ℃, and the carbon defect-containing and oxygen-doped carbon nitride photocatalytic material is obtained after the pure-phase carbon nitride is cooled to the room temperature. The preparation method of the carbon defect-containing and oxygen-doped carbon nitride material can avoid the agglomeration and stacking phenomenon of the nano material. The preparation method is simple, time-saving, green, environment-friendly, energy-saving and controllable, and has a large specific surface area and abundant surface reaction sites. Under the condition of visible light, the material can efficiently remove tetracycline antibiotics in the water body and has excellent stability.
Description
Technical Field
The invention relates to a preparation technology of a photocatalytic material, in particular to preparation of a carbon defect and oxygen-doped carbon nitride photocatalytic material and application of the carbon defect and oxygen-doped carbon nitride photocatalytic material in removal of tetracycline antibiotics in a water body.
Background
In addition to traditional pollutants, emerging micropollutants emerging in recent years have received increasing attention. Emerging micropollutants include primarily pharmaceuticals and personal care products, endocrine disruptors, drinking water disinfection byproducts, artificial sweeteners, ionic liquids, and the like. Antibiotic drugs are one of the important members of the family of drugs and personal care products, and are widely used for preventing and treating various diseases because they can prevent animals and plants from being infected by bacteria. Antibiotics are difficult to decompose in ecological environments such as animal and plant bodies, water bodies, soil and the like, mainly enter the environment in the form of original drugs or metabolites to cause pollution problems, and bring serious threats to human health, diet and sanitary environment.
The current methods for removing antibiotic contaminants mainly include chemical methods, physical methods, biological methods and other complex combined methods. Practice shows that the conventional method is difficult to remove high-concentration organic pollutants and sewage with deep color with high efficiency and low cost, and usually needs the participation of advanced oxidation technology. The photocatalysis technology is a novel oxidation technology with low energy consumption, high efficiency and environmental protection, and provides a new idea and a new way for removing antibiotics in a water body environment.
Carbon nitride is an organic carbon material rich in carbon and nitrogen elements, and can be subjected to visible light response and corrosion resistance by acid, alkali and strong oxidizing substances. Carbon nitride is mainly prepared by thermal polymerization of monomers containing carbon and nitrogen elements, but the solid-phase polymerization reaction has the defects of uneven heat and mass transfer, so that the specific surface area of the carbon nitride is small, the recombination rate of photo-generated electron-hole pairs is high, the number of surface reaction sites is insufficient, and the photocatalytic activity is not ideal. In order to overcome the above disadvantages, researchers have adopted various strategies. For example, patent publication No. CN112892611A reports a preparation method of fish scale tubular carbon nitride and the application of the method in photocatalytic removal of organic pollutants. Dissolving trithiocyanuric acid and melamine in an organic solvent respectively, mixing, filtering, drying, and calcining the mixture to synthesize the fish scale tubular carbon nitride nano material. For another example, patent publication No. CN112871195A discloses a method for preparing a carbon nitride photocatalyst with a multi-morphological structure. The method comprises the steps of respectively dissolving melamine and cyanuric acid in a solvent, then mixing the two solutions, dispersing a solid in an inorganic salt solution after separation, and finally obtaining the carbon nitride photocatalytic nano material with various morphological structures through freezing, drying and calcining. And a preparation method of a high-efficiency carbon self-doped graphite phase carbon nitride visible-light-induced photocatalyst is reported in a patent with the publication number of CN 106902859A. The visible light catalyst takes melamine as a precursor, organic micromolecules with different carbon-nitrogen element ratios as a self-doping carbon source, and the carbon self-doping graphite phase carbon nitride nano material is prepared by vacuum heat treatment copolymerization after full mixing. The carbon nitride nano material with different appearance structures and excellent performance is prepared by the method, but the preparation method has more complicated steps, involves the use of organic solvents, has certain influence on the environment and has higher cost. Based on the method, the carbon nitride nano photocatalytic material with excellent performance is synthesized by a green, environment-friendly, economical and simple method.
Disclosure of Invention
The invention aims to solve the existing problems, provides a preparation method of a carbon nitride photocatalytic material doped with carbon defects and oxygen, and applies the photocatalytic material to the removal of tetracycline in a water body environment. The method has the advantages of simplicity, high efficiency, environmental protection, energy conservation and controllability, can be used for large-scale mass synthesis of carbon defect and oxygen-doped carbon nitride nano materials, has unique sea urchin bionic structure and anisotropy, and shows excellent removal efficiency and long-term stability to tetracycline.
The technical problem of the invention is mainly solved by the following technical scheme: a preparation method of carbon nitride photocatalytic material doped with carbon defects and oxygen is characterized by comprising the following steps:
(1) uniformly grinding the urea crystals into fine particles;
(2) placing the fine particles in an alumina crucible, and covering the alumina crucible with a cover while keeping good sealing performance;
(3) sealing the crucible, feeding the crucible into a quartz tube furnace, heating the crucible to 550 ℃ from room temperature by a heating program of 5 ℃/min, sintering, and keeping the constant temperature for 3 hours;
(4) cooling to room temperature after the sintering process is naturally finished, taking out a light yellow sample, and grinding the light yellow sample into a light yellow powder to obtain a pure-phase Carbon Nitride (CN) photocatalytic material;
(5) the pure phase Carbon Nitride (CN) photocatalytic material was dispersed in an aqueous solvent, transferred to a teflon liner, sealed and maintained at 180 ℃ for 4, 6, 8 and 10 hours, and the resulting samples were named: CNO-4, CNO-6 and CNO-10.
In the preparation method of the carbon defect and oxygen doped carbon nitride photocatalytic material, in the step (1), the purity of the urea used is analytically pure.
In the preparation method of the carbon defect and oxygen doped carbon nitride photocatalytic material, in the step (1), the device for grinding urea is a ball mill, the working speed is 100 rmp, and the time is 24 hours.
In the preparation method of the carbon defect and oxygen doped carbon nitride photocatalytic material, in the step (2), the material used for sealing the alumina crucible is tin foil paper with the thickness of 0.3-0.5 microns.
In the preparation method of the carbon defect and oxygen doped carbon nitride photocatalytic material, in the step (3), the temperature rise program is 6 ℃/min, the heating temperature rise atmosphere is air, the atmospheric pressure is kept at 100.6 kPa, and the humidity is constant at 40%.
In the preparation method of the carbon defect and oxygen doped carbon nitride photocatalytic material, in the step (4), the temperature is increased from 20 ℃ to 550 ℃ in the urea sintering process, the temperature increase rate is 5 ℃/min, and the temperature is kept at 550 ℃ for 3 hours.
In the preparation method of the carbon defect and oxygen doped carbon nitride photocatalytic material, in the step (5), the water used for dispersing the pure phase carbon nitride photocatalytic material (CN) is deionized water, and the conductivity is 18.2 MW-cm-1Simultaneous ultrasound assistanceAnd dispersing CN.
In the preparation method of the carbon defect and oxygen doped carbon nitride photocatalytic material, in the step (5), the polytetrafluoroethylene hydrothermal reactor is heated to be an oven, and the heating time is 4, 6, 8 and 10 hours.
A preparation method of a carbon defect and oxygen doped carbon nitride photocatalytic material and application of the carbon defect and oxygen doped carbon nitride photocatalytic material in removal of antibiotics in a water body are characterized in that the antibiotics are tetracycline, and the application of the antibiotics comprises the following steps:
(1) uniformly grinding the urea crystals into fine particles;
(2) placing the fine particles in an alumina crucible, and covering the alumina crucible with a cover while keeping good sealing performance;
(3) sealing the crucible, feeding the crucible into a quartz tube furnace, heating the crucible to 550 ℃ from room temperature by a heating program of 5 ℃/min, sintering, and keeping the constant temperature for 3 hours;
(4) after the sintering process is naturally finished, cooling to room temperature, taking out a light yellow sample, and grinding the light yellow sample into light yellow powder to obtain a pure-phase Carbon Nitride (CN) photocatalytic material;
(5) dispersing a pure-phase Carbon Nitride (CN) photocatalytic material into a water solvent, transferring the pure-phase Carbon Nitride (CN) photocatalytic material into a polytetrafluoroethylene lining, sealing the polytetrafluoroethylene lining, and keeping the polytetrafluoroethylene lining at 180 ℃ for several hours;
(6) under the conditions of visible light and room temperature, the carbon defect and oxygen doped carbon nitride photocatalytic material is applied to the removal of tetracycline solution (20 mg/L) in a water body, an ultraviolet spectrophotometer is utilized to monitor the change of the tetracycline concentration, and meanwhile, the residual concentration of the tetracycline and the removal efficiency are calculated.
Compared with the existing method for preparing carbon nitride, the method has the following remarkable beneficial effects:
(1) the carbon-defect and oxygen-doped carbon nitride photocatalytic nanomaterial can be controllably prepared by a monomer thermal polymerization, solvation and hydrothermal method, has the advantages of three-dimensional open structure, large specific surface area and high separation efficiency of photo-generated electron-hole pairs, and can avoid the phenomenon of agglomeration and stacking of the nanomaterial;
(2) the method is simple in preparation, time-saving, green, environment-friendly, energy-saving and controllable, is expected to be applied to the production of high-activity three-dimensional open carbon nitride nano-materials on a large scale, and has practical application value;
(3) the scheme can be used for simply, in-situ and controllably preparing the nanoscale three-dimensional carbon nitride sea urchin material, has a large specific surface area, is rich in surface reactions as points, shows anisotropic characteristics, can be used for efficiently removing tetracycline in a water body, and has long-term structural stability;
(4) has excellent photocatalytic activity, visible light condition and room temperature condition, can eliminate tetracycline in about 90% in 20 min, and has degrading efficiency higher than that of pure phase carbon nitride photocatalyst and other multicomponent composite catalysts.
Drawings
FIG. 1 is a scanning electron microscope representation of the invention, i.e., a scanning electron microscope picture of pure phase Carbon Nitride (CN). Wherein, FIG. 1 (a) and FIG. 1 (b) are both scanning electron micrographs of CN; the lower right corner of fig. 1 (a) to 1 (b) is a scale.
FIG. 2 is a scanning electron microscope depiction of a carbon defect-containing and oxygen-doped carbon nitride material according to the present invention. Wherein, FIG. 2 (a) and FIG. 1 (b) are both scanning electron micrographs of CNO-6; the lower right corner of fig. 2 (a) -2 (b) is a scale.
FIG. 3 shows the UV-visible diffuse reflectance spectra of CN and CNO-6. Wherein the ordinate of fig. 3 is absorbance (Abs), the abscissa is Wavelength (Wavelength), and the unit is nm; the upper bit line represents CN and the lower bit line represents CNO-6.
FIG. 4 is a fluorescence spectrum of CN and CNO-6 of the present invention. In fig. 4, the ordinate is intensity, the abscissa is Wavelength (Wavelength), the unit is nm, the upper line represents CN, and the lower line represents CNO-6.
FIG. 5 is a graph of the catalytic performance and first order reaction kinetics constants of photocatalytic degradation of tetracycline by CN, CNO-4, CNO-6, CNO-8 and CNO-10 of the present invention. Wherein, FIG. 5 (a) is a catalytic performance diagram of the photocatalytic degradation of tetracycline by CN, CNO-4, CNO-6, CNO-8 and CNO-10, the ordinate is tetracycline concentration/tetracycline initial concentration, the abscissa is time, and the unit is minute (min); is justThe squares, circles, upper triangles, lower triangles and diamonds represent CN, CNO-4, CNO-6, CNO-8 and CNO-10, respectively. FIG. 5 (b) is the first order reaction kinetic constants for N, CNO-4, CNO-6, CNO-8 and CNO-10 photocatalytic degradation of tetracycline, plotted on the ordinate as kinetic (K) constants in units of: min(s)-1The abscissa is the respective catalyst.
Detailed Description
The technical solution of the present invention is further described in detail by the following embodiments, which are only specific examples, but the scope of the present invention is not limited thereto.
A preparation method of carbon defect-containing and oxygen-doped carbon nitride (CNO-6) photocatalytic material comprises the following steps:
(1) uniformly grinding the urea crystals into fine particles;
(2) placing the fine particles in an alumina crucible, and covering the alumina crucible with a cover while keeping good sealing performance;
(3) sealing the crucible, feeding the crucible into a quartz tube furnace, heating the crucible to 550 ℃ from room temperature by a heating program of 5 ℃/min, sintering, and keeping the constant temperature for 3 hours;
(4) cooling to room temperature after the sintering process is naturally finished, taking out a light yellow sample, and grinding the light yellow sample into a light yellow powder to obtain a pure-phase Carbon Nitride (CN) photocatalytic material;
(5) dispersing a pure-phase Carbon Nitride (CN) photocatalytic material into a water solvent, transferring the material into a polytetrafluoroethylene lining, sealing the lining, and keeping the lining at 180 ℃ for several hours to obtain samples which are respectively named as: CNO-4, CNO-6 and CNO-10.
One of the embodiments is as follows: the application of the carbon nitride photocatalytic material containing carbon defects and oxygen doping in removing antibiotics in water bodies is that the antibiotics are tetracycline, and the application is as follows:
(1) dispersing 25 mg of carbon nitride photocatalytic material containing carbon defects and oxygen defects into deionized water;
(2) adding a certain mass of tetracycline powder into the water body, and blending into a tetracycline solution of 20 mg/L;
(3) strongly stirring for more than 30 minutes in a dark environment and then carrying out ultrasonic treatment for about 10 minutes;
(4) transferring the mixed solution in the last step into a quartz reactor, and externally connecting circulating condensed water to keep the temperature of the solution at 5 ℃;
(5) a xenon lamp simulating sunlight is used as a light source, a filter is added to obtain visible light for exciting a photocatalytic reaction, and reaction liquid is stirred at the same time; the change of the tetracycline concentration was monitored by an ultraviolet spectrophotometer, while calculating the residual concentration of tetracycline and the efficiency of removal.
The characterization was carried out using CN and CNO-6 as catalysts as follows.
Firstly, performing scanning electron microscope characterization on CN, and displaying the results as shown in FIG. 1 (a) and FIG. 1 (b): CN presents a random particle structure, and the size is from hundreds of nanometers (nm) to microns (mum);
the CNO-6 was characterized by scanning electron microscopy, as shown in FIGS. 2 (a) and 2(b), and the results showed: CN presents a three-dimensional open sea urchin structure, nano-level needles are uniformly planted on the surface of large particles to form a unique sea urchin structure, and the size of the sea urchin is about 10 mu m.
Secondly, performing element analysis on CN and CNO-6 samples by using the energy scattering spectrometer, and finding that the content of C elements in the CNO-6 samples is obviously lower than that of C in the CN, which indicates that C defects are formed in the CNO-6; furthermore, the O content reached 6.7 a.t% in CNO-6, which is much higher than 0.9 a.t% in CN, indicating that the C defect formed was replaced by O element. Based on the energy scattering spectrum results, we thus concluded that CNO-6 possesses surface states containing carbon defects and oxygen doping. The correlation results are shown in table 1.
Table 1 the elemental contents of CN and CNO were determined from energy scattering spectroscopy.
| C (a.t%) | N (a.t%) | O (a.t%) | |
| CN | 42.6 | 56.5 | 0.9 |
| CNO-6 | 33.4 | 59.9 | 6.7 |
And thirdly, performing ultraviolet-visible diffuse reflection spectrum analysis on CN and CNO-6, wherein the result is shown in figure 3.
In FIG. 3 CN and CNO-6 show greater light absorption at 461 nm and 449 nm, thus calculating energy bandwidths of 2.78 eV and 2.85 eV, respectively.
From the above analysis, it can be seen that carbon defect and oxygen-doped carbon nitride (CNO-6) prepared by the present method and Carbon Nitride (CN) prepared by the conventional method maintain similar UV-visible response characteristics.
Fourthly, the CN and the CNO-6 are subjected to fluorescence spectrum analysis, and the result is shown in figure 4.
In the fluorescence spectrum shown in FIG. 4, the fluorescence emission peaks of CN and CNO-6 are both in the range of 420-480 nm, which indicates that CN and CNO-6 have closer energy bandwidths.
In the fluorescence spectrum curve shown in FIG. 4, the fluorescence emission peak intensity of CN is much greater than that of CNO-6, indicating that CN generates higher recombination rate of photo-generated electron-hole pairs than CNO-6.
And fifthly, CN and CNO-6 are applied to the research of removing tetracycline in the water environment by visible light catalysis:
respectively dispersing 25 mg of CN and CNO-6 into 100 mL of solution with the concentration of 20 mg/L of tetracycline, stirring, externally connecting circulating water, keeping the temperature of the reactor at 5 ℃, and shading for at least 30 minutes to achieve the adsorption-desorption balance of the tetracycline on the surface of the CNO-6;
placing the above solutions containing CN and CNO-6 into xenon lamp light source, filtering the xenon lamp light source to obtain visible light (λ)>420 nm), light intensity of 100 mW/cm2；
The solution is stirred moderately and the rotating speed of a stirrer is controlled to be 80 rmp;
preparing a stopwatch and zeroing;
the stopwatch is quickly pressed down while the light source is turned on, and the timing is started;
taking 3 mL of sample every 20 min, centrifuging (4000 rmp,25 min), taking supernatant, filtering (a water-based filter membrane with the pore size of 0.02 mu m), and finally measuring the concentration change by using an ultraviolet spectrophotometer;
the concentration measured each time is recorded as C, the original concentration is recorded as Co, wherein Co is a fixed value which is the initial concentration (20 mg/L) of tetracycline;
statistics were performed using concentration/initial concentration (C/Co) as the ordinate value, time as the abscissa, and unit in minutes (min). As shown by the circular line in FIG. 5 (a), the CNO-6 has the highest efficiency of removing tetracycline by photocatalysis, and can remove about 90% of tetracycline within 20 min;
the fitting was performed with the concentration/initial concentration (C/Co) as the target, taking the negative logarithm as the ordinate, time as the abscissa, and the unit being minutes (min). As shown in FIG. 5 (b), the kinetics constants for tetracycline removal of CN, CNO-4, CNO-6, CNO-4 and CNO-10 reached 0.034 min-1、0.047 min-1、0.040 min-1、0.033 min-1And 0.027 min-1。
As shown in FIG. 5 (a), the removal efficiency of carbon defect-containing and oxygen-doped carbon nitride material (CNO-6) is superior to that of carbon nitride prepared by the conventional method, which indicates that the method can synthesize high-performance carbon nitride photocatalytic material.
Sixthly, applying CNO-6 to photocatalytic cycle removal of tetracycline in water environment:
repeating the fourth experiment, using a carbon defect-containing and oxygen-doped carbon nitride (CNO-6) photocatalyst to remove tetracycline in the water body, and calculating a kinetic constant for removing tetracycline and a tetracycline removal rate in each cycle experiment;
the experiment of the fourth step is repeated for 5 times, the carbon defect-containing and oxygen-doped carbon nitride (CNO-6) photocatalyst can be recycled, and no obvious attenuation occurs, which shows that the carbon nitride is expected to be used for a long time to remove tetracycline and has great economic value.
Seventhly, applying CNO-6 to a mechanism for removing tetracycline in the water body through photocatalysis circulation:
based on the above experimental results of one to five items, we propose a mechanism for photocatalytic tetracycline removal: under the irradiation of visible light, the light excites CNO-6 to generate electron-hole (e)--h+) Para, migration and separation to CNO-6 surface, and participation of electron in formation of superoxide radical (. O)2 -) Hydroxyl free radical (. OH) and oxidizes tetracycline into intermediates, and further oxidizes and mineralizes tetracycline and the intermediates thereof to generate carbon dioxide and water peak small molecules; void (h)+) And also participate in the oxidation and mineralization reaction of the tetracycline to generate small molecules such as carbon dioxide, water and the like, so that the tetracycline is completely removed.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (7)
1. A preparation method of carbon nitride photocatalytic material doped with carbon defects and oxygen is characterized by comprising the following steps:
(1) uniformly grinding the urea crystals into fine particles by using a ball mill;
(2) placing the fine particles in an alumina crucible, and covering the alumina crucible with a cover while keeping good sealing performance;
(3) sealing the crucible, feeding the crucible into a quartz tube furnace, heating the crucible to 550 ℃ from room temperature by a heating program of 5 ℃/min, sintering, and keeping the constant temperature for 3 hours;
(4) cooling to room temperature after the sintering process is naturally finished, taking out a light yellow sample, and grinding the light yellow sample into light yellow powder to obtain a pure-phase Carbon Nitride (CN) photocatalytic material;
(5) the pure phase Carbon Nitride (CN) photocatalytic material was dispersed in an aqueous solvent, transferred to a teflon liner, sealed and kept at 180 ℃ for 4, 6, 8 and 10 hours, respectively, and the resulting samples were named: CNO-4, CNO-6 and CNO-10.
2. The method for preparing a carbon defect-containing and oxygen-doped carbon nitride photocatalytic material according to claim 1, wherein in the step (1), the urea purity is analytical grade.
3. The method for preparing carbon defect-containing and oxygen-doped carbon nitride photocatalytic material according to claim 1, wherein in the step (1), the device for grinding urea is a ball mill, the operating speed is 100 rmp, and the time is 24 hours.
4. The method of claim 1, wherein the alumina crucible is sealed with a thickness of 0.3-0.5 μm in step (2).
5. The method for preparing carbon nitride photocatalytic material containing carbon defect and oxygen doping according to claim 1, wherein in the step (3), the apparatus for thermal polymerization of fine urea particles is a quartz tube furnace, the temperature during thermal polymerization of fine urea particles is raised from 20 ℃ to 550 ℃, the temperature raising procedure is 5 ℃/min, and the constant temperature time is 3 hours.
6. The method as claimed in claim 1, wherein the hydrothermal reaction of pure-phase Carbon Nitride (CN) in step (5) is carried out at 180 deg.C for 4, 6, 8 and 10 hours.
7. The use of the carbon defect-containing and oxygen-doped carbon nitride photocatalytic material as claimed in any one of claims 1 to 6 for removing antibiotics in a water body, wherein the antibiotics are tetracycline, and the use comprises the following steps:
(1) dispersing 25 mg of the synthesized carbon nitride photocatalytic material containing carbon defects and oxygen defects into deionized water;
(2) adding a certain mass of tetracycline powder into the water body, and blending into a tetracycline solution of 20 mg/L;
(3) strongly stirring for more than 30 minutes in a dark environment and then carrying out ultrasonic treatment for about 10 minutes;
(4) transferring the mixed solution in the last step into a quartz reactor, and externally connecting circulating condensed water to keep the temperature of the solution at 5 ℃;
(5) a xenon lamp simulating sunlight is used as a light source, a filter is added to obtain visible light for exciting a photocatalytic reaction, and reaction liquid is stirred at the same time; the change of the tetracycline concentration was monitored by an ultraviolet spectrophotometer, while calculating the residual concentration of tetracycline and the efficiency of removal.
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