CN114950520B - CeO (CeO) 2 Na, K doped g-C 3 N 4 Fenton-like catalytic material and preparation method and application thereof - Google Patents
CeO (CeO) 2 Na, K doped g-C 3 N 4 Fenton-like catalytic material 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The application provides a Fenton-like catalytic material, a preparation method and application thereof, and in particular relates to CeO 2 Na, K doped g-C 3 N 4 Fenton-like catalytic material, wherein CeO is 2 Cubic phase, g-C 3 N 4 In a lamellar/lamellar structure, na and K are doped in g-C 3 N 4 Interlayer, the CeO 2 Na, K doped g-C 3 N 4 Catalytic material and H 2 O 2 Can efficiently degrade tetracycline hydrochloride under the combined action of no illumination and wide pH range, and can overcome the defects that the traditional Fenton reaction produces pig iron mud, can only be used under acidic condition, and the like in the catalysis process. g-C in the present application 3 N 4 With CeO 2 A strong interaction occurs such that the surface Ce 4+ The electrons are enriched around to become active centers, and the electrons and the active centers act synergistically to obviously improve the catalytic oxidation activity of the catalyst. The preparation method provided by the application has the advantages of simple process, good repeatability and suitability for industrial production.
Description
Technical Field
The application relates to the technical field of inorganic composite materials, in particular to CeO 2 Na, K doped g-C 3 N 4 Fenton-like catalytic material, preparation method thereof and application thereof in efficiently degrading tetracycline hydrochloride.
Background
With the development of economy, water pollution is increasingly serious, and the pollution becomes a serious social problem threatening human health and sustainable development of economy.
Antibiotics (also called antibiotics) are drugs which have the effects of inhibiting and killing pathogenic microorganisms such as bacteria, fungi, spirochetes, mycoplasma, chlamydia and the like. It has been reported that total amounts of about 10 to 20 ten thousand tons are used throughout the world, with at least 50% of antibiotics being used in animal husbandry and aquaculture. Tetracyclines are one of the antibiotics, and have the advantages of broad spectrum, high quality, low cost and the like, and have become antibiotics with large production and clinical use amounts. But tetracycline is difficult to be absorbed by intestines and stomach of animals, most of the tetracycline is discharged in a form of a parent compound, water solubility is good, the tetracycline is difficult to be biodegraded in the environment, and residual medicines in soil are easy to be washed by rain water to enter water or sink into bottom mud for storage and enrichment.
Antibiotics in water environment have certain toxicity to aquatic organisms, and can inhibit or kill pathogenic microorganisms, meanwhile, also inhibit the activity of beneficial microorganisms in the environment, seriously influence the material circulation of an ecosystem, remain and accumulate in organisms, enter human bodies along with food chains, and have potential harm to human health, so that the removal of organic pollutants difficult to degrade in the antibiotic wastewater becomes a research hot spot and a difficult point in the environmental field.
As a high-grade green oxidation technology, fenton catalytic oxidation reaction utilizes hydroxyl free radicals with strong oxidability to thoroughly mineralize toxic organic pollutants which are difficult to decompose into non-toxic CO 2 、H 2 Small molecular substances such as O and the like, and simultaneously, the method has the characteristics of simple process, safety, green, low cost and the like, so that the method is widely researched and applied to remove various organic pollutants.
The common Fenton catalyst is an iron-containing compound, the homogeneous iron-containing Fenton catalyst has the problem that a large amount of iron mud is generated due to iron ion loss in the actual use process to cause secondary pollution, and meanwhile, the problem only applicable to an acidic solution exists, so that the Fenton catalyst is usually prepared into a heterogeneous catalyst to improve the stability, for example, chinese patent CN201910812311.0 discloses an iron-containing Fenton heterogeneous multicomponent solid phase catalyst and a preparation method thereof, for example, chinese patent CN201910670448.7 discloses a preparation method of a magnetic visible light heterogeneous iron-containing Fenton catalyst, and Chinese patent 201910874037.X provides FeVO for photo-Fenton combined catalysis 4 /TiO 2 Etc. However, the existing heterogeneous iron-containing Fenton catalyst has the problem of insufficient activity. And can produce iron mud and other pollutants. And is simply g-C 3 N 4 The photocatalyst can be used for degrading pollutants, but needs to be carried out under the condition of illumination, and cannot be carried out in the absence of light (at night, in cloudy days or in dark places)) Degrading the pollutants.
Therefore, the development of a novel heterogeneous Fenton-like catalyst has become a subject of a research hotspot in the environmental field
Disclosure of Invention
In order to solve the problems, a novel CeO with high efficiency is provided 2 Na, K co-doping g-C 3 N 4 Heterogeneous Fenton-like catalytic material, preparation method and application thereof, and catalyst under no-light condition and H 2 O 2 Can efficiently oxidize and decompose the tetracycline hydrochloride within a wider pH range under the synergistic effect, and provides a new idea and solution for efficient and green pollutant treatment.
The specific technical scheme is as follows:
a first aspect of the present application is to provide a CeO 2 Na, K doped g-C 3 N 4 The preparation method of the Fenton-like catalytic material has the characteristics that the preparation method comprises the following steps:
step 1): calcining urea in a muffle furnace at 500 ℃ for 2h, then heating to 530 ℃ at a heating rate of 2 ℃/min, then calcining again for 2h, cooling to room temperature, grinding to powder, and then calcining in the muffle furnace at 550 ℃ for 3h at a heating rate of 5 ℃/min to obtain g-C 3 N 4 ；
Step 2): cerium nitrate, sodium nitrite, potassium nitrate and g-C prepared in the step 1) 3 N 4 Mixing and grinding according to a certain proportion, roasting in air atmosphere, washing with hot water to remove residual ions, separating and drying to obtain the CeO 2 Na, K doped g-C 3 N 4 Fenton-like catalytic materials.
The preparation method also has the characteristics that cerium nitrate, sodium nitrite, potassium nitrate and g-C in the step 2) 3 N 4 The mixing mass ratio of (2) is 1:1:1.9 (1.0-2.0).
The preparation method also has the characteristics that the roasting method in the step 2) is as follows: heating to 250-350 deg.c at the heating rate of 2 deg.c/min for roasting for 1-3 hr.
The preparation method also has the characteristics that the drying temperature in the step 2) is 60-80 ℃ and the drying time is 8-12h.
A second aspect of the present application is to provide a CeO 2 Na, K doped g-C 3 N 4 Fenton-like catalytic material has the characteristics and is prepared according to the preparation method.
CeO as described above 2 Na, K doped g-C 3 N 4 Fenton-like catalytic material also has the characteristic that CeO in the catalytic material 2 In cubic phase, g-C 3 N 4 In a lamellar/lamellar structure, na and K are doped in g-C 3 N 4 Interlaminar layers.
CeO prepared by the application 2 Na, K co-doping g-C 3 N 4 Heterogeneous Fenton-like catalytic material comprises CeO 2 And Na, K co-doping g-C 3 N 4 Two catalytically active components; wherein, ceO 2 Co-doping g-C with Na, K in cubic phase and particle size of tens of nanometers to several micrometers 3 N 4 The catalyst is a novel Fenton-like catalyst with a nano-sheet/lamellar structure and is light-resistant and H-shaped 2 O 2 Can efficiently oxidize and decompose the tetracycline hydrochloride under the synergistic effect, and can be used in a wider pH range. The composite catalytic material is also used for removing other organic pollutants.
CeO provided by the application 2 Na, K co-doping g-C 3 N 4 The catalytic mechanism of heterogeneous Fenton-like catalytic materials may be: na, K co-doping to give g-C 3 N 4 Has more single electrons and CeO 2 After compounding, ceO 2 Co-doping with Na, K g-C 3 N 4 There is strong interaction between them, electron co-doping g-C from Na, K 3 N 4 Transfer to CeO 2 On, so that the surface Ce 4+ Enriching electrons around to become an active center; at the same time, surface Ce 4+ And Ce (Ce) 3+ Will also be with H 2 O 2 Hydroxyl radicals, singlet oxygen molecules and superoxide anion radicals, which react with strong oxidizing properties, which react with organic pollutants to CO 2 And H 2 Small molecule products such as O.
A third aspect of the present application provides the above CeO 2 Na, K dopingMiscellaneous g-C 3 N 4 Fenton-like catalytic material is used for catalyzing tetracycline hydrochloride (molecular formula is C 22 H 25 ClN 2 O 8 CAS number 64-75-5).
The application also has the characteristic that the catalytic tetracycline hydrochloride is degraded into the catalytic degradation of the tetracycline hydrochloride under the dark condition and the wide pH value.
The beneficial effect of above-mentioned scheme is:
1. CeO provided by the application 2 Na, K co-doping g-C 3 N 4 Heterogeneous Fenton-like catalytic material and H 2 O 2 Under the combined action, the catalyst material has high matt catalytic oxidation activity, and can be used at night/dark places as compared with a pure photocatalytic material;
2. CeO provided by the application 2 Na, K co-doping g-C 3 N 4 The heterogeneous Fenton-like catalytic material is a novel Fenton-like catalyst, the catalytic mechanism of the heterogeneous Fenton-like catalytic material is different from that of the iron-containing Fenton catalyst, and bad consequences such as pig iron mud and the like can not be generated; ceO in the catalytic material provided by the application 2 And Na, K co-doping g-C 3 N 4 Are all catalytically active and have a strong interaction with each other, so that the surface Ce 4+ The electrons are enriched around to become active centers, and the active species such as singlet oxygen with long service life and strong oxidability are generated by the synergistic effect of the electrons and the active species, so that the catalytic oxidation activity of the catalyst is obviously improved;
3. the preparation method provided by the application has the advantages of simple process, environment friendliness, readily available raw materials, good repeatability and suitability for industrial production;
4. CeO provided by the application 2 Na, K co-doping g-C 3 N 4 The heterogeneous Fenton-like catalytic material has high efficiency of catalyzing the degradation of tetracycline hydrochloride and can be used in a wider pH range.
Drawings
FIG. 1 shows CeO prepared in example 1 of the present application 2 Na, K co-doping g-C 3 N 4 Scanning electron microscopy of heterogeneous Fenton-like catalytic materials.
Detailed Description
The following description of the embodiments of the present application will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other.
The application is further described below with reference to the drawings and specific examples, which are not intended to be limiting.
Example 1
CeO (CeO) 2 Na, K doped g-C 3 N 4 The preparation of the Fenton-like catalytic material comprises the following steps:
step 1): weighing a certain amount of urea, placing into a crucible with a cover, placing the crucible into a muffle furnace, calcining at 500 ℃ for 2 hours, heating to 530 ℃ at a speed of 2 ℃/min, calcining again for 2 hours, cooling to room temperature, and obtaining blocky g-C 3 N 4 Grinding to powder, putting into a muffle furnace again, heating to 550 ℃ at a speed of 5 ℃/min, and calcining for 3 hours to obtain light yellow g-C 3 N 4 A powder;
step 2): ce (NO) 3 ) 3 ·6H 2 O、KNO 3 、NaNO 2 g-C prepared 3 N 4 Mixing according to a mass ratio of 1:1:1.9:1.5, fully grinding to obtain a uniform precursor, placing the precursor in a muffle furnace, heating to 350 ℃ at 2 ℃/min, calcining for 3 hours, cooling to room temperature, washing with hot water to remove residual ions, washing with absolute ethyl alcohol for three times, and drying in a baking oven at 60 ℃ for 12 hours to obtain CeO 2 Na, K doped g-C 3 N 4 Fenton-like catalytic materials.
As shown in FIG. 1, the above CeO 2 Na, K doped g-C 3 N 4 CeO in Fenton-like catalytic material 2 The particle size of the/CN catalyst is 10-30 nm, g-C 3 N 4 Is a sheetLayered structure.
XRD tests showed that the above CeO was shown 2 Na, K doped g-C 3 N 4 CeO in Fenton-like catalytic material 2 Is a cubic phase.
Example 2
CeO (CeO) 2 Na, K doped g-C 3 N 4 The preparation of the Fenton-like catalytic material comprises the following steps:
step 1): weighing a certain amount of urea, placing into a crucible with a cover, placing the crucible into a muffle furnace, calcining at 500 ℃ for 2 hours, heating to 530 ℃ at a speed of 2 ℃/min, calcining again for 2 hours, cooling to room temperature, and obtaining blocky g-C 3 N 4 Grinding to powder, putting into a muffle furnace again, heating to 550 ℃ at a speed of 5 ℃/min, and calcining for 3 hours to obtain light yellow g-C 3 N 4 A powder;
step 2): ce (NO) 3 ) 3 ·6H 2 O、KNO 3 、NaNO 2 g-C prepared 3 N 4 Mixing according to a mass ratio of 1:1:1.9:1.5, fully grinding to obtain a uniform precursor, placing the precursor in a muffle furnace, heating to 300 ℃ at a speed of 2 ℃/min, calcining for 3 hours, cooling to room temperature, washing with hot water to remove residual ions, washing with absolute ethyl alcohol for three times, and drying in a baking oven at 60 ℃ for 12 hours to obtain CeO 2 Na, K doped g-C 3 N 4 Fenton-like catalytic materials.
Example 3
CeO (CeO) 2 Na, K doped g-C 3 N 4 The preparation of the Fenton-like catalytic material comprises the following steps:
step 1): weighing a certain amount of urea, placing into a crucible with a cover, placing the crucible into a muffle furnace, calcining at 500 ℃ for 2 hours, heating to 530 ℃ at a speed of 2 ℃/min, calcining again for 2 hours, cooling to room temperature, and obtaining blocky g-C 3 N 4 Grinding to powder, putting into a muffle furnace again, heating to 550 ℃ at a speed of 5 ℃/min, and calcining for 3 hours to obtain light yellow g-C 3 N 4 A powder;
step 2): ce (NO) 3 ) 3 ·6H 2 O、KNO 3 、NaNO 2 Preparation and preparationg-C of (2) 3 N 4 Mixing according to a mass ratio of 1:1:1.9:1.5, fully grinding to obtain a uniform precursor, placing the precursor in a muffle furnace, heating to 250 ℃ at a speed of 2 ℃/min, calcining for 3 hours, cooling to room temperature, washing with hot water to remove residual ions, washing with absolute ethyl alcohol for three times, and drying in a baking oven at 60 ℃ for 12 hours to obtain CeO 2 Na, K doped g-C 3 N 4 Fenton-like catalytic materials.
Example 4
CeO (CeO) 2 Na, K doped g-C 3 N 4 The preparation of the Fenton-like catalytic material comprises the following steps:
step 1): weighing a certain amount of urea, placing into a crucible with a cover, placing the crucible into a muffle furnace, calcining at 500 ℃ for 2 hours, heating to 530 ℃ at a speed of 2 ℃/min, calcining again for 2 hours, cooling to room temperature, and obtaining blocky g-C 3 N 4 Grinding to powder, putting into a muffle furnace again, heating to 550 ℃ at a speed of 5 ℃/min, and calcining for 3 hours to obtain light yellow g-C 3 N 4 A powder;
step 2): ce (NO) 3 ) 3 ·6H 2 O、KNO 3 、NaNO 2 g-C prepared 3 N 4 Mixing according to a mass ratio of 1:1:1.9:1.5, fully grinding to obtain a uniform precursor, placing the precursor in a muffle furnace, heating to 350 ℃ at 2 ℃/min, calcining for 1h, cooling to room temperature, washing with hot water to remove residual ions, washing with absolute ethyl alcohol for three times, and drying in a baking oven at 60 ℃ for 12h to obtain CeO 2 Na, K doped g-C 3 N 4 Fenton-like catalytic materials.
Example 5
CeO (CeO) 2 Na, K doped g-C 3 N 4 The preparation of the Fenton-like catalytic material comprises the following steps:
step 1): weighing a certain amount of urea, placing into a crucible with a cover, placing the crucible into a muffle furnace, calcining at 500 ℃ for 2 hours, heating to 530 ℃ at a speed of 2 ℃/min, calcining again for 2 hours, cooling to room temperature, and obtaining blocky g-C 3 N 4 Grinding to powder, placing into a muffle furnace again, heating to 550deg.C at a rate of 5deg.C/min, and calcining for 3 hr to obtainTo pale yellow g-C 3 N 4 A powder;
step 2): ce (NO) 3 ) 3 ·6H 2 O、KNO 3 、NaNO 2 g-C prepared 3 N 4 Mixing according to a mass ratio of 1:1:1.9:1.5, fully grinding to obtain a uniform precursor, placing the precursor in a muffle furnace, heating to 350 ℃ at 2 ℃/min, calcining for 5 hours, cooling to room temperature, washing with hot water to remove residual ions, washing with absolute ethyl alcohol for three times, and drying in a baking oven at 60 ℃ for 12 hours to obtain CeO 2 Na, K doped g-C 3 N 4 Fenton-like catalytic materials.
Example 6
CeO (CeO) 2 Na, K doped g-C 3 N 4 The preparation of the Fenton-like catalytic material comprises the following steps:
step 1): weighing a certain amount of urea, placing into a crucible with a cover, placing the crucible into a muffle furnace, calcining at 500 ℃ for 2 hours, heating to 530 ℃ at a speed of 2 ℃/min, calcining again for 2 hours, cooling to room temperature, and obtaining blocky g-C 3 N 4 Grinding to powder, putting into a muffle furnace again, heating to 550 ℃ at a speed of 5 ℃/min, and calcining for 3 hours to obtain light yellow g-C 3 N 4 A powder;
step 2): ce (NO) 3 ) 3 ·6H 2 O、KNO 3 、NaNO 2 g-C prepared 3 N 4 Mixing according to a mass ratio of 1:1:1.9:1.0, fully grinding to obtain a uniform precursor, placing the precursor in a muffle furnace, heating to 350 ℃ at 2 ℃/min, calcining for 3 hours, cooling to room temperature, washing with hot water to remove residual ions, washing with absolute ethyl alcohol for three times, and drying in a baking oven at 60 ℃ for 12 hours to obtain CeO 2 Na, K doped g-C 3 N 4 Fenton-like catalytic materials.
Example 7
CeO (CeO) 2 Na, K doped g-C 3 N 4 The preparation of the Fenton-like catalytic material comprises the following steps:
step 1): weighing a certain amount of urea, placing the urea into a crucible with a cover, placing the crucible into a muffle furnace, calcining at 500 ℃ for 2 hours, and then adding the urea at 2 ℃/miHeating to 530 ℃ at n rate, calcining for 2h again, cooling to room temperature, and obtaining blocky g-C 3 N 4 Grinding to powder, putting into a muffle furnace again, heating to 550 ℃ at a speed of 5 ℃/min, and calcining for 3 hours to obtain light yellow g-C 3 N 4 A powder;
step 2): ce (NO) 3 ) 3 ·6H 2 O、KNO 3 、NaNO 2 g-C prepared 3 N 4 Mixing according to a mass ratio of 1:1:1.9:2.0, fully grinding to obtain a uniform precursor, placing the precursor in a muffle furnace, heating to 350 ℃ at 2 ℃/min, calcining for 3 hours, cooling to room temperature, washing with hot water to remove residual ions, washing with absolute ethyl alcohol for three times, and drying in an oven at 80 ℃ for 8 hours to obtain CeO 2 Na, K doped g-C 3 N 4 Fenton-like catalytic materials.
Comparative example 1
Weighing a certain amount of urea, placing into a crucible with a cover, placing into a muffle furnace, calcining at 500 ℃ for 2 hours, heating to 530 ℃ at 2 ℃/min, calcining again for 2 hours, cooling to room temperature, and obtaining blocky g-C 3 N 4 Grinding to powder, putting into a muffle furnace again, heating to 550 ℃ at a speed of 5 ℃/min, calcining for 3 hours, and finally obtaining light yellow g-C 3 N 4 And (3) powder.
Comparative example 2
Weighing a certain amount of urea, placing into a crucible with a cover, placing into a muffle furnace, calcining at 500 ℃ for 2 hours, heating to 530 ℃ at 2 ℃/min, calcining again for 2 hours, cooling to room temperature, and obtaining blocky g-C 3 N 4 Grinding to powder, putting into a muffle furnace again, heating to 550 ℃ at a speed of 5 ℃/min, and calcining for 3 hours to obtain light yellow g-C 3 N 4 A powder; to KNO 3 、NaNO 2 g-C prepared as described above 3 N 4 Mixing according to a mass ratio of 1:1:1.5, fully grinding to obtain a uniform precursor, placing the precursor in a muffle furnace, heating to 350 ℃ at 2 ℃/min, calcining for 3 hours, cooling to room temperature, washing with hot water and absolute ethyl alcohol in sequence for three times, and drying in a 60 ℃ oven for 12 hours to obtain Na and K co-doped g-C 3 N 4 A catalyst.
Comparative example 3
Fe synthesized by hydrothermal method 2 O 3 : quantity of FeCl 3 ·6H 2 O is added into deionized water to form solution A; adding ammonium acetate to ethanol to form a solution b; then adding the solution a into the solution b, continuously stirring for 60 minutes, transferring the mixed solution into an autoclave, heating to 180 ℃ for reaction for 18 hours, separating and drying to obtain Fe 2 O 3 A catalyst.
Comparative example 4
Ce (NO) 3 ) 3 ·6H 2 O and KNO 3 、NaNO 2 Mixing according to a mass ratio of 1:1:1.9, fully grinding to obtain a uniform precursor, then placing the precursor into a muffle furnace, heating to 350 ℃ at 2 ℃/min, calcining for 3 hours, cooling to room temperature, washing with hot water and absolute ethyl alcohol for three times in sequence, and then drying in an oven at 60 ℃ for 12 hours to obtain light yellow CeO 2 A catalyst.
Comparative example 5
Commercial CeO 2 Comparative examples were made.
In order to examine the degradation effect of the catalyst prepared in the examples and the comparative examples in the catalytic oxidation of tetracycline hydrochloride, the present inventors tested the degradation performance of tetracycline hydrochloride according to the following method, and the test process is as follows: 50mg of the catalyst samples prepared in the examples and comparative examples were dispersed in a solution of tetracycline hydrochloride (70 mg/L) at 40℃and 200. Mu. L H was added 2 O 2 The reaction is carried out for 0.5 hour under the conditions of light shielding and different pH values, and the catalyst activity is obtained by measuring the concentration change of the tetracycline hydrochloride by an ultraviolet-visible spectrophotometry.
The reaction rate constants of the catalysts prepared in examples 1 to 7 and comparative examples 1 to 3 of the present application for catalytic oxidation of tetracycline hydrochloride degradation under different reaction conditions are shown in the following table.
The above table shows that the CeO provided by the application 2 Na, K co-doping g-C 3 N 4 Fenton-like composite catalytic material can be used for matt and H 2 O 2 Can effectively oxidize and decompose tetracycline hydrochloride under the existence condition; as can be seen from the test results of the numbers 1 to 3, ceO 2 Na, K co-doping g-C 3 N 4 The applicable pH range of the Fenton-like composite catalytic material catalytic degradation reaction is wider (pH=4.0-9.1); as can be seen from comparison of test results of serial numbers 1, 4, 5, 6 and 7, ceO obtained by different preparation methods 2 Na, K co-doping g-C 3 N 4 The Fenton-like composite catalytic material has different catalytic degradation rate constants; as can be seen from comparison of test results of serial numbers 1, 10, 11, 12, 13 and 14, ag 3 PO 4 /g-C 3 N 4 The catalytic degradation effect of the Fenton-like composite catalytic material is better than that of g-C 3 N 4 Is also superior to g-C 3 N 4 、Fe 2 O 3 CeO alone 2 And Na, K co-doping g-C 3 N 4 Catalytic material and commercial CeO 2 。
The foregoing description is only illustrative of the preferred embodiments of the present application and is not to be construed as limiting the scope of the application, and it will be appreciated by those skilled in the art that equivalent substitutions and obvious variations may be made using the description and illustrations of the present application, and are intended to be included within the scope of the present application.
Claims (8)
1. CeO (CeO) 2 Na, K doped g-C 3 N 4 The preparation method of the Fenton-like catalytic material is characterized by comprising the following steps of:
step 1): calcining urea in a muffle furnace at 500 ℃ for 2h, then heating to 530 ℃ at a heating rate of 2 ℃/min, then calcining again for 2h, cooling to room temperature, grinding to powder, and then calcining in the muffle furnace at 550 ℃ for 3h at a heating rate of 5 ℃/min to obtain g-C 3 N 4 ；
Step 2): nitric acid is added toCerium, sodium nitrite, potassium nitrate and g-C prepared in step 1) 3 N 4 Mixing and grinding according to a certain proportion, roasting in air atmosphere, washing with hot water to remove residual ions, separating and drying to obtain the CeO 2 Na, K doped g-C 3 N 4 Fenton-like catalytic materials.
2. The method according to claim 1, wherein cerium nitrate, sodium nitrite, potassium nitrate and g-C in step 2) 3 N 4 The mixing mass ratio of (2) is 1:1:1.9 (1.0-2.0).
3. The method according to claim 1, wherein the firing method in step 2) is: heating to 250-350 deg.c at the heating rate of 2 deg.c/min for roasting for 1-3 hr.
4. The process according to claim 1, wherein the drying temperature in step 2) is 60 to 80 ℃ and the drying time is 8 to 12 hours.
5. CeO (CeO) 2 Na, K doped g-C 3 N 4 Fenton-like catalytic material, which is characterized by being prepared by the preparation method according to any one of claims 1-4.
6. CeO according to claim 5 2 Na, K doped g-C 3 N 4 Fenton-like catalytic material is characterized in that CeO in the catalytic material 2 In cubic phase, g-C 3 N 4 In a lamellar/lamellar structure, na and K are doped in g-C 3 N 4 Interlaminar layers.
7. The CeO of claim 5 or 6 2 Na, K doped g-C 3 N 4 The Fenton-like catalytic material is applied to catalyzing the degradation of tetracycline hydrochloride.
8. The use according to claim 7, wherein said catalytic tetracycline hydrochloride degradation is catalytic degradation of tetracycline hydrochloride under light-shielding conditions and at a broad pH.
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