CN114950520A - CeO (CeO) 2 Doped with Na, K g-C 3 N 4 Fenton-like catalytic material and preparation method and application thereof - Google Patents
CeO (CeO) 2 Doped with Na, K g-C 3 N 4 Fenton-like catalytic material and preparation method and application thereof Download PDFInfo
- Publication number
- CN114950520A CN114950520A CN202210372849.6A CN202210372849A CN114950520A CN 114950520 A CN114950520 A CN 114950520A CN 202210372849 A CN202210372849 A CN 202210372849A CN 114950520 A CN114950520 A CN 114950520A
- Authority
- CN
- China
- Prior art keywords
- ceo
- fenton
- doped
- catalytic material
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- 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
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention provides a Fenton-like catalytic material, a preparation method and application thereof, and particularly relates to CeO 2 Doped with Na, K g-C 3 N 4 Fenton-like catalytic material, in which is CeO 2 Cubic phase, g-C 3 N 4 Is in a sheet/layer structure, Na and K are doped in g-C 3 N 4 Interlaminar layer of the CeO 2 Doped with Na, K g-C 3 N 4 Catalytic material and H 2 O 2 Under the combined action, the tetracycline hydrochloride can be efficiently degraded under the condition of no illumination and in a wide pH range, and the defects that iron mud is generated by the traditional Fenton reaction and can only be used under the acidic condition and the like can be overcome in the catalytic process. In this application g-C 3 N 4 With CeO 2 Strong interaction occurs so that surface Ce 4+ Electrons are enriched around the catalyst to form an active center, and the two have synergistic effect to obviously improve the catalytic oxidation activity of the catalyst. The preparation method provided by the invention has the advantages of simple process, good repeatability and suitability for industrial production.
Description
Technical Field
The invention relates to the technical field of inorganic composite materials, in particular to CeO 2 Doped with Na, K 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 body pollution becomes more serious, and the method becomes a great social problem threatening human health and sustainable economic development.
Antibiotics (also called antibiotics) are a class of drugs which have the effects of inhibiting and killing pathogenic microorganisms such as bacteria, fungi, spirochetes, mycoplasma, chlamydia and the like. The total annual use of antibiotics in the world is reported to be about 10-20 ten thousand tons, and at least 50% of the antibiotics are used in animal husbandry and aquaculture. Tetracycline is one of antibiotics, has the advantages of broad spectrum, high quality and low price, and the like, and has become an antibiotic with large production capacity and clinical use amount. However, tetracycline is difficult to be absorbed by intestines and stomach of animals, most of tetracycline is discharged in the form of parent compounds, the tetracycline is good in water solubility and is not easy to be biodegraded in the environment, and residual drugs in soil are easy to be washed by rainwater and enter water or sink into sediment for storage and enrichment.
Antibiotics in the water environment have certain toxicity to organisms in water, inhibit the activity of beneficial microorganisms in the environment while inhibiting or killing pathogenic microorganisms, seriously influence the substance circulation of an ecological system, remain and accumulate in organisms, enter human bodies along with food chains and have potential harm to the health of the human bodies, and therefore, the removal of organic pollutants which are difficult to degrade in antibiotic wastewater becomes a research hotspot and difficulty in the environmental field.
As a high-grade green oxidation technology, Fenton catalytic oxidation reaction utilizes hydroxyl free radicals with strong oxidizing property to thoroughly mineralize toxic organic pollutants which are difficult to decompose into nonhazardous CO 2 、H 2 O and other small molecular substances, and has the characteristics of simple process, safety, greenness, low cost and the like, so that the method is widely researched and used for removing various organic pollutants.
The common Fenton catalyst is an iron-containing compound, the homogeneous phase iron-containing Fenton catalyst has the problems of iron ion loss and generation of a large amount of iron mud to cause secondary pollution in the actual use process, and the homogeneous phase iron-containing Fenton catalyst is only suitable for an acid solution, so the homogeneous phase iron-containing Fenton catalyst is usually prepared into a heterogeneous phase catalyst to improve the stability of the heterogeneous phase catalyst, for example, the heterogeneous phase catalyst is prepared in the Chinese patent CN201910812311.0An iron-containing Fenton heterogeneous multi-component solid-phase catalyst and a preparation method thereof are disclosed, 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 And the like. However, the existing heterogeneous iron-containing Fenton catalyst has the problem of insufficient activity. And generate iron sludge and other pollutants. And simple 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 degrade the pollutants in the absence of light (at night, in cloudy days or in dark places).
Therefore, the development of a novel heterogeneous Fenton-like catalyst becomes a research hotspot in the environmental field
Disclosure of Invention
Aiming at the problems, the invention provides a high-efficiency novel CeO 2 /Na, K codoped g-C 3 N 4 Heterogeneous Fenton-like catalytic material, preparation method and application thereof, and catalyst under dark condition and H 2 O 2 Under the synergistic effect of the compounds, the tetracycline hydrochloride can be efficiently oxidized and decomposed within a wider pH range, and a new idea and solution are provided for efficient and green pollutant treatment.
The specific technical scheme is as follows:
in a first aspect of the present invention, there is provided a CeO 2 Doped with Na, K 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, heating to 530 ℃ at a heating rate of 2 ℃/min, calcining for 2h again, cooling to room temperature, grinding to powder, placing in the muffle furnace again, heating to 550 ℃ at a heating rate of 5 ℃/min, calcining for 3h to obtain g-C 3 N 4 ；
Step 2): cerium nitrate, sodium nitrite, potassium nitrate and g-C prepared in step 1) 3 N 4 Mixing according to a certain proportion, grinding, roasting in air atmosphere, washing with hot water to remove residual ions, separating and drying to obtain CeO 2 /Na, K doping with g-C 3 N 4 Fenton-like catalytic material.
The above-mentioned production method is also characterized in that cerium nitrate, sodium nitrite, potassium nitrate and g-C in the step 2) 3 N 4 The mixing mass ratio of (1: 1: 1.9) (1.0-2.0).
The above preparation method is also characterized in that the roasting method in the step 2) is as follows: heating to 250-350 ℃ at the heating rate of 2 ℃/min and roasting for 1-3 h.
The preparation method is also characterized in that the drying temperature in the step 2) is 60-80 ℃, and the drying time is 8-12 h.
In a second aspect of the present invention, there is provided a CeO 2 Doped with Na, K g-C 3 N 4 Fenton-like catalytic material, having such characteristics, prepared according to the above preparation method.
CeO as defined above 2 Doped with Na, K g-C 3 N 4 Fenton-like catalytic material, also having the feature that CeO is present in said catalytic material 2 Is a cubic phase, g-C 3 N 4 Is in a sheet/layer structure, Na and K are doped in g-C 3 N 4 Between the layers.
CeO prepared by the invention 2 /Na, K codoped g-C 3 N 4 The heterogeneous Fenton-like catalytic material comprises CeO 2 Co-doping of g-C with Na, K 3 N 4 Two catalytically active components; wherein, CeO 2 Is cubic phase, has particle size of tens of nanometers to several micrometers, and is doped with Na and K 3 N 4 Is of a nano-sheet/layered structure, and the catalyst is a novel Fenton-like catalyst and is protected from light and H 2 O 2 Can efficiently oxidize and decompose tetracycline hydrochloride under the synergistic effect of the components, and can be used in a wider pH range. The composite catalytic material is also used for removing other organic pollutants.
The CeO provided by the invention 2 /Na, K codoped g-C 3 N 4 The catalysis mechanism of the heterogeneous Fenton-like catalytic material is probably as follows: co-doping of Na and K to make g-C 3 N 4 With more single electrons, with CeO 2 After compounding, CeO 2 Codoping of g-C with Na, K 3 N 4 Has strong interaction, electrons are codoped from Na and K to g-C 3 N 4 Transfer to CeO 2 To make the surface Ce 4+ Electrons are enriched around the active center; at the same time, surface Ce 4+ And Ce 3+ Will also react with H 2 O 2 Hydroxyl radical, singlet oxygen molecule and superoxide anion radical with strong oxidizing property are reacted, and the active species convert organic pollutants into CO 2 And H 2 O and other small molecular products.
The third aspect of the present invention is to provide the above-mentioned CeO 2 Doped with Na, K g-C 3 N 4 Fenton-like catalytic material 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 under the condition of keeping away from light and under the condition of wide pH value.
The beneficial effect of above-mentioned scheme is:
1. the CeO provided by the invention 2 /Na, K codoped g-C 3 N 4 Heterogeneous Fenton-like catalytic material and H 2 O 2 Under the combined action, the photocatalyst has high non-photocatalytic oxidation activity, and compared with a pure photocatalyst, the photocatalyst can be used at night/in dark;
2. the CeO provided by the invention 2 /Na, K codoped 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 Fe-containing Fenton-like catalyst, and adverse effects such as iron mud and the like can not be generated; CeO in the catalytic material provided by the invention 2 Co-doping of g-C with Na, K 3 N 4 All have catalytic activity, and strong interaction occurs between the two, so that the surface Ce is formed 4+ Electrons are enriched around the catalyst to form an active center, and the two active centers generate active species such as singlet oxygen with normal service life and strong oxidizing property under the synergistic action, so that the catalytic oxidation activity of the catalyst is remarkably improved;
3. the preparation method provided by the invention has the advantages of simple process, environmental protection, easily available raw materials, good repeatability and suitability for industrial production;
4. the CeO provided by the invention 2 /Na, K codoped g-C 3 N 4 The heterogeneous Fenton-like catalytic material has high degradation efficiency in catalyzing tetracycline hydrochloride, and can be used in a wide pH range.
Drawings
FIG. 1 shows CeO prepared in example 1 of the present invention 2 /Na, K codoped g-C 3 N 4 Scanning electron microscopy of heterogeneous Fenton-like catalytic materials.
Detailed Description
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, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive efforts based on the embodiments of the present invention, shall fall within the scope of protection of the present invention.
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The invention is further described with reference to the following drawings and specific examples, which are not intended to be limiting.
Example 1
CeO (CeO) 2 Doped with Na, K g-C 3 N 4 The Fenton-like catalytic material is prepared by the following steps:
step 1): weighing a certain amount of urea and placing the urea in a crucible with a cover, placing the crucible in a muffle furnace to calcine for 2h at 500 ℃, then heating to 530 ℃ at the speed of 2 ℃/min and then calcining for 2h again, cooling to room temperature, and obtaining block g-C 3 N 4 Grinding to powder, placing into muffle furnace, heating to 550 deg.C at 5 deg.C/min, and calcining for 3 hr to obtain light yellow g-C 3 N 4 Powder;
step 2): adding Ce (NO) 3 ) 3 ·6H 2 O、KNO 3 、NaNO 2 And g-C of preparation 3 N 4 Fully grinding the mixture after mixing according to the mass ratio of 1:1:1.9:1.5 to obtain a uniform precursor, then placing the precursor in a muffle furnace, heating to 350 ℃ at the speed of 2 ℃/min, calcining for 3h, cooling to room temperature, washing with hot water to remove residual ions, washing with absolute ethyl alcohol for three times, drying in an oven at the temperature of 60 ℃ for 12h to obtain CeO 2 Doped with Na, K g-C 3 N 4 Fenton-like catalytic material.
As shown in FIG. 1, the above-mentioned CeO 2 Doped with Na, K g-C 3 N 4 CeO in Fenton-like catalytic material 2 The particle size of the/CN catalyst is 10-30 nanometers, g-C 3 N 4 In a sheet/layer structure.
XRD test shows that the CeO is prepared from the above-mentioned materials 2 Doped with Na, K g-C 3 N 4 CeO in Fenton-like catalytic material 2 Is a cubic phase.
Example 2
CeO (CeO) 2 Doped with Na, K g-C 3 N 4 The Fenton-like catalytic material is prepared by the following steps:
step 1): weighing a certain amount of urea and placing the urea in a crucible with a cover, placing the crucible in a muffle furnace to calcine for 2h at 500 ℃, then heating to 530 ℃ at the speed of 2 ℃/min to calcine for 2h again, cooling to room temperature, and obtaining block g-C 3 N 4 Grinding to powder, placing into muffle furnace again, heating to 550 deg.C at 5 deg.C/min, calcining for 3 hr to obtain light yellow g-C 3 N 4 Powder;
step 2): adding Ce (NO) 3 ) 3 ·6H 2 O、KNO 3 、NaNO 2 And g-C of preparation 3 N 4 Fully grinding the mixture after mixing according to the mass ratio of 1:1:1.9:1.5 to obtain a uniform precursor, then placing the precursor in a muffle furnace, heating to 300 ℃ at the speed of 2 ℃/min, calcining for 3h, cooling to room temperature, washing with hot water to remove residual ions, washing with absolute ethyl alcohol for three times, drying in an oven at the temperature of 60 ℃ for 12h to obtain CeO 2 Doped with Na, K g-C 3 N 4 Fenton-like catalytic material.
Example 3
CeO (CeO) 2 Doped with Na, K g-C 3 N 4 Fenton-like catalytic materialThe preparation method comprises the following steps:
step 1): weighing a certain amount of urea and placing the urea in a crucible with a cover, placing the crucible in a muffle furnace to calcine for 2h at 500 ℃, then heating to 530 ℃ at the speed of 2 ℃/min to calcine for 2h again, cooling to room temperature, and obtaining block g-C 3 N 4 Grinding to powder, placing into muffle furnace again, heating to 550 deg.C at 5 deg.C/min, calcining for 3 hr to obtain light yellow g-C 3 N 4 Powder;
step 2): adding Ce (NO) 3 ) 3 ·6H 2 O、KNO 3 、NaNO 2 And g-C of preparation 3 N 4 Fully grinding the mixture after mixing according to the mass ratio of 1:1:1.9:1.5 to obtain a uniform precursor, then placing the precursor in a muffle furnace, heating to 250 ℃ at the speed of 2 ℃/min, calcining for 3h, cooling to room temperature, washing with hot water to remove residual ions, washing with absolute ethyl alcohol for three times, drying in an oven at the temperature of 60 ℃ for 12h to obtain CeO 2 Doped with Na, K g-C 3 N 4 Fenton-like catalytic material.
Example 4
CeO (CeO) 2 Na, K doped g-C 3 N 4 The Fenton-like catalytic material is prepared by the following steps:
step 1): weighing a certain amount of urea, placing the urea in a crucible with a cover, placing the crucible in a muffle furnace, calcining for 2h at 500 ℃, heating to 530 ℃ at the speed of 2 ℃/min, calcining for 2h again, cooling to room temperature, and obtaining block g-C 3 N 4 Grinding to powder, placing into muffle furnace again, heating to 550 deg.C at 5 deg.C/min, calcining for 3 hr to obtain light yellow g-C 3 N 4 A powder;
step 2): adding Ce (NO) 3 ) 3 ·6H 2 O、KNO 3 、NaNO 2 And g-C of preparation 3 N 4 Fully grinding the mixture after mixing according to the mass ratio of 1:1:1.9:1.5 to obtain a uniform precursor, then placing the precursor in a muffle furnace, heating to 350 ℃ at the speed of 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, drying in an oven at the temperature of 60 ℃ for 12h to obtain CeO 2 Doped with Na, K g-C 3 N 4 Fenton-like catalytic material.
Example 5
CeO (CeO) 2 Doped with Na, K g-C 3 N 4 The Fenton-like catalytic material is prepared by the following steps:
step 1): weighing a certain amount of urea and placing the urea in a crucible with a cover, placing the crucible in a muffle furnace to calcine for 2h at 500 ℃, then heating to 530 ℃ at the speed of 2 ℃/min to calcine for 2h again, cooling to room temperature, and obtaining block g-C 3 N 4 Grinding to powder, placing into muffle furnace again, heating to 550 deg.C at 5 deg.C/min, calcining for 3 hr to obtain light yellow g-C 3 N 4 Powder;
step 2): adding Ce (NO) 3 ) 3 ·6H 2 O、KNO 3 、NaNO 2 And g-C of preparation 3 N 4 Fully grinding the mixture after mixing according to the mass ratio of 1:1:1.9:1.5 to obtain a uniform precursor, then placing the precursor in a muffle furnace, heating to 350 ℃ at the speed of 2 ℃/min, calcining for 5h, cooling to room temperature, washing with hot water to remove residual ions, washing with absolute ethyl alcohol for three times, drying in an oven at the temperature of 60 ℃ for 12h to obtain CeO 2 Na, K doped g-C 3 N 4 Fenton-like catalytic material.
Example 6
CeO (CeO) 2 Doped with Na, K g-C 3 N 4 The Fenton-like catalytic material is prepared by the following steps:
step 1): weighing a certain amount of urea and placing the urea in a crucible with a cover, placing the crucible in a muffle furnace to calcine for 2h at 500 ℃, then heating to 530 ℃ at the speed of 2 ℃/min to calcine for 2h again, cooling to room temperature, and obtaining block g-C 3 N 4 Grinding to powder, placing into muffle furnace again, heating to 550 deg.C at 5 deg.C/min, calcining for 3 hr to obtain light yellow g-C 3 N 4 Powder;
step 2): ce (NO) 3 ) 3 ·6H 2 O、KNO 3 、NaNO 2 And g-C of preparation 3 N 4 Fully grinding the mixture after mixing according to the mass ratio of 1:1:1.9:1.0 to obtain a uniform precursor, and then placing the precursor in a muffle furnace to raise the temperature at 2 ℃/minCalcining at 350 deg.C for 3h, cooling to room temperature, washing with hot water to remove residual ions, washing with anhydrous ethanol for three times, and drying in oven at 60 deg.C for 12h to obtain CeO 2 Na, K doped g-C 3 N 4 Fenton-like catalytic material.
Example 7
CeO (CeO) 2 Doped with Na, K g-C 3 N 4 The Fenton-like catalytic material is prepared by the following steps:
step 1): weighing a certain amount of urea and placing the urea in a crucible with a cover, placing the crucible in a muffle furnace to calcine for 2h at 500 ℃, then heating to 530 ℃ at the speed of 2 ℃/min to calcine for 2h again, cooling to room temperature, and obtaining block g-C 3 N 4 Grinding to powder, placing into muffle furnace again, heating to 550 deg.C at 5 deg.C/min, calcining for 3 hr to obtain light yellow g-C 3 N 4 Powder;
step 2): adding Ce (NO) 3 ) 3 ·6H 2 O、KNO 3 、NaNO 2 And g-C of preparation 3 N 4 Fully grinding the mixture after mixing according to the mass ratio of 1:1:1.9:2.0 to obtain a uniform precursor, then placing the precursor in a muffle furnace, heating to 350 ℃ at a speed of 2 ℃/min, calcining for 3h, cooling to room temperature, washing with hot water to remove residual ions, washing with absolute ethyl alcohol for three times, drying in an oven at 80 ℃ for 8h to obtain CeO 2 Doped with Na, K g-C 3 N 4 Fenton-like catalytic material.
Comparative example 1
Weighing a certain amount of urea, placing the urea in a crucible with a cover, placing the crucible in a muffle furnace, calcining for 2h at 500 ℃, heating to 530 ℃ at a speed of 2 ℃/min, calcining for 2h again, cooling to room temperature, and obtaining block g-C 3 N 4 Grinding to powder, putting into muffle furnace again, heating to 550 deg.C at 5 deg.C/min, calcining for 3 hr to obtain yellowish g-C 3 N 4 And (3) powder.
Comparative example 2
Weighing a certain amount of urea, placing the urea in a crucible with a cover, placing the crucible in a muffle furnace, calcining for 2h at 500 ℃, heating to 530 ℃ at a speed of 2 ℃/min, calcining for 2h again, cooling to room temperature, and obtaining block g-C 3 N 4 Grinding to powder, placing into muffle furnace, heating to 550 deg.C at 5 deg.C/min, and calcining for 3 hr to obtain light yellow g-C 3 N 4 A powder; mixing KNO 3 、NaNO 2 With g-C prepared as described above 3 N 4 Fully grinding the mixture according to the mass ratio of 1:1:1.5 to obtain a uniform precursor, then placing the precursor in a muffle furnace, heating to 350 ℃ at a speed of 2 ℃/min, calcining for 3h, cooling to room temperature, washing with hot water and absolute ethyl alcohol for three times, and drying in an oven at 60 ℃ for 12h to obtain Na and K codoped g-C 3 N 4 A catalyst.
Comparative example 3
Hydrothermal synthesis of Fe 2 O 3 : a certain amount of FeCl 3 ·6H 2 Adding O into deionized water to form a solution A; adding ammonium acetate into ethanol to form a solution b; adding the solution a into the solution b, continuously stirring for 60 minutes, transferring the mixed solution into an autoclave, heating to 180 ℃, reacting for 18 hours, separating and drying to obtain Fe 2 O 3 A catalyst.
Comparative example 4
Adding Ce (NO) 3 ) 3 ·6H 2 O and KNO 3 、NaNO 2 Mixing the components according to a mass ratio of 1:1:1.9, fully grinding to obtain a uniform precursor, then placing the precursor in a muffle furnace, heating to 350 ℃ at a speed of 2 ℃/min, calcining for 3h, cooling to room temperature, washing with hot water and absolute ethyl alcohol sequentially for three times, and drying in a 60 ℃ oven for 12h 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 embodiment and the comparative example in the catalytic oxidation of tetracycline hydrochloride, the inventor tests 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 different examples and comparative examples were dispersed in a solution of tetracycline hydrochloride (70mg/L) at 40 ℃ and 200. mu. L H was added 2 O 2 Reacting for 0.5 hour under the conditions of light shielding and different pH valuesThe concentration change of the tetracycline hydrochloride is measured by an ultraviolet-visible spectrophotometry method to obtain the activity of the catalyst.
The degradation rate constants of the catalysts prepared in examples 1 to 7 and comparative examples 1 to 3 of the present invention for catalytic oxidation of tetracycline hydrochloride under different reaction conditions are shown in the following table.
The above table shows that the CeO provided by the present invention 2 /Na, K codoped g-C 3 N 4 The Fenton-like composite catalytic material can be used in the absence of light and H 2 O 2 Can effectively oxidize and decompose tetracycline hydrochloride under the existing condition; as is clear from the test results of Nos. 1 to 3, CeO 2 /Na, K codoped g-C 3 N 4 The applicable pH range of the Fenton-like composite catalytic material catalytic degradation reaction is wide (the pH is 4.0-9.1); as is clear from comparison of test results of Nos. 1, 4, 5, 6 and 7, CeO was obtained by different preparation methods 2 /Na, K codoped g-C 3 N 4 The Fenton-like composite catalytic material has different catalytic degradation rate constants; as is clear from comparison of test results of Nos. 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 obviously better than that of g-C 3 N 4 Is also superior to g-C 3 N 4 、Fe 2 O 3 Pure CeO 2 Co-doping of g-C with Na, K 3 N 4 Catalytic material and commercial CeO 2 。
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention.
Claims (8)
1. CeO (CeO) 2 Doped with Na, K 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, heating to 530 ℃ at a heating rate of 2 ℃/min, calcining for 2h again, cooling to room temperature, grinding to powder, placing in the muffle furnace again, heating to 550 ℃ at a heating rate of 5 ℃/min, calcining for 3h to obtain g-C 3 N 4 ；
Step 2): cerium nitrate, sodium nitrite, potassium nitrate and g-C prepared in step 1) 3 N 4 Mixing according to a certain proportion, grinding, roasting in air atmosphere, washing with hot water to remove residual ions, separating and drying to obtain CeO 2 Doped with Na, K g-C 3 N 4 Fenton-like catalytic material.
2. The method according to claim 1, wherein the cerium nitrate, the sodium nitrite, the potassium nitrate and g-C in the step 2) 3 N 4 The mixing mass ratio of (1: 1: 1.9), (1.0-2.0).
3. The preparation method according to claim 1, wherein the roasting method in the step 2) is as follows: heating to 250-350 ℃ at the heating rate of 2 ℃/min and roasting for 1-3 h.
4. The method 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 Doped with Na, K g-C 3 N 4 Fenton-like catalytic material, characterized in that it is prepared according to the preparation method of any one of claims 1 to 4.
6. The CeO of claim 5 2 Doped with Na, K g-C 3 N 4 Fenton-like catalytic material, characterized in that the catalytic material isCeO in 2 Is a cubic phase, g-C 3 N 4 Is in a sheet/layer structure, Na and K are doped in g-C 3 N 4 Between the layers.
7. CeO according to claim 5 or 6 2 Doped with Na, K 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 the catalyzed degradation of tetracycline hydrochloride is catalyzed degradation of tetracycline hydrochloride under conditions protected from light and at a broad pH.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210372849.6A CN114950520B (en) | 2022-04-11 | 2022-04-11 | CeO (CeO) 2 Na, K doped g-C 3 N 4 Fenton-like catalytic material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210372849.6A CN114950520B (en) | 2022-04-11 | 2022-04-11 | CeO (CeO) 2 Na, K doped g-C 3 N 4 Fenton-like catalytic material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114950520A true CN114950520A (en) | 2022-08-30 |
| CN114950520B CN114950520B (en) | 2023-10-03 |
Family
ID=82978321
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210372849.6A Active CN114950520B (en) | 2022-04-11 | 2022-04-11 | CeO (CeO) 2 Na, K doped g-C 3 N 4 Fenton-like catalytic material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114950520B (en) |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103301867A (en) * | 2013-06-25 | 2013-09-18 | 重庆工商大学 | Inorganic ion doped carbon nitride photocatalyst and preparation method thereof |
| CN105148975A (en) * | 2015-09-30 | 2015-12-16 | 安徽工业大学 | Preparation method and application of potassium-doped mesoporous g-C3N4 photocatalytic material |
| CN106955727A (en) * | 2017-04-14 | 2017-07-18 | 中国石油大学(华东) | The g C that a kind of surface is modified3N4Preparation |
| CN107774294A (en) * | 2017-11-14 | 2018-03-09 | 阜阳师范学院 | A kind of novel photochemical catalyst K g C3N4And its prepare and apply |
| CN108940338A (en) * | 2018-07-09 | 2018-12-07 | 湖南大学 | Potassium element adulterates nitride porous carbon photochemical catalyst and its preparation method and application |
| CN110240133A (en) * | 2019-07-03 | 2019-09-17 | 辽宁科技大学 | Potassium ion doped graphite phase carbon nitride nanosheet photocatalyst and preparation method thereof |
| CN110665531A (en) * | 2019-10-23 | 2020-01-10 | 江汉大学 | Pt/g-C3N4/CeO2Composite photocatalyst and preparation method and application thereof |
| CN110732338A (en) * | 2019-10-25 | 2020-01-31 | 湖北工业大学 | Carbon nanowire/g-C3N4Composite visible light catalyst and preparation method thereof |
| CN111889126A (en) * | 2020-06-28 | 2020-11-06 | 南昌大学 | Preparation method and application of Fenton-like material with visible light response |
| CN112090438A (en) * | 2020-08-07 | 2020-12-18 | 苏州科技大学 | BiOCl/g-C3N4/CeO2Synthesis method of three-phase photocatalytic material |
| CN112264071A (en) * | 2020-10-26 | 2021-01-26 | 江汉大学 | g-C3N4@CeO2Preparation method and application of composite catalyst |
| CN112266666A (en) * | 2020-09-17 | 2021-01-26 | 赵梓俨 | Photocatalytic environment-friendly coating for purifying air pollutants and preparation method thereof |
| CN112473712A (en) * | 2020-11-23 | 2021-03-12 | 南京大学 | CeO treated with different atmospheres2/g-C3N4Heterojunction material, preparation method and application thereof |
| CN112920663A (en) * | 2021-03-05 | 2021-06-08 | 赵梓俨 | Antifouling self-cleaning coating and preparation method thereof |
| CN112958130A (en) * | 2021-02-05 | 2021-06-15 | 吉林大学 | Catalyst for photocatalysis and preparation method and application thereof |
-
2022
- 2022-04-11 CN CN202210372849.6A patent/CN114950520B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103301867A (en) * | 2013-06-25 | 2013-09-18 | 重庆工商大学 | Inorganic ion doped carbon nitride photocatalyst and preparation method thereof |
| CN105148975A (en) * | 2015-09-30 | 2015-12-16 | 安徽工业大学 | Preparation method and application of potassium-doped mesoporous g-C3N4 photocatalytic material |
| CN106955727A (en) * | 2017-04-14 | 2017-07-18 | 中国石油大学(华东) | The g C that a kind of surface is modified3N4Preparation |
| CN107774294A (en) * | 2017-11-14 | 2018-03-09 | 阜阳师范学院 | A kind of novel photochemical catalyst K g C3N4And its prepare and apply |
| CN108940338A (en) * | 2018-07-09 | 2018-12-07 | 湖南大学 | Potassium element adulterates nitride porous carbon photochemical catalyst and its preparation method and application |
| CN110240133A (en) * | 2019-07-03 | 2019-09-17 | 辽宁科技大学 | Potassium ion doped graphite phase carbon nitride nanosheet photocatalyst and preparation method thereof |
| CN110665531A (en) * | 2019-10-23 | 2020-01-10 | 江汉大学 | Pt/g-C3N4/CeO2Composite photocatalyst and preparation method and application thereof |
| CN110732338A (en) * | 2019-10-25 | 2020-01-31 | 湖北工业大学 | Carbon nanowire/g-C3N4Composite visible light catalyst and preparation method thereof |
| CN111889126A (en) * | 2020-06-28 | 2020-11-06 | 南昌大学 | Preparation method and application of Fenton-like material with visible light response |
| CN112090438A (en) * | 2020-08-07 | 2020-12-18 | 苏州科技大学 | BiOCl/g-C3N4/CeO2Synthesis method of three-phase photocatalytic material |
| CN112266666A (en) * | 2020-09-17 | 2021-01-26 | 赵梓俨 | Photocatalytic environment-friendly coating for purifying air pollutants and preparation method thereof |
| CN112264071A (en) * | 2020-10-26 | 2021-01-26 | 江汉大学 | g-C3N4@CeO2Preparation method and application of composite catalyst |
| CN112473712A (en) * | 2020-11-23 | 2021-03-12 | 南京大学 | CeO treated with different atmospheres2/g-C3N4Heterojunction material, preparation method and application thereof |
| CN112958130A (en) * | 2021-02-05 | 2021-06-15 | 吉林大学 | Catalyst for photocatalysis and preparation method and application thereof |
| CN112920663A (en) * | 2021-03-05 | 2021-06-08 | 赵梓俨 | Antifouling self-cleaning coating and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 杨婷婷 等: "CeO2/g-C3N4光催化-芬顿高效降解盐酸强力霉素", 环境工程学报 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114950520B (en) | 2023-10-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109364939B (en) | Method for removing antibiotics by using biochar loaded ferro-manganese bimetallic oxide photo-Fenton composite material | |
| de Moraes et al. | Effect of Nb/C ratio in the morphological, structural, optical and photocatalytic properties of novel and inexpensive Nb2O5/carbon xerogel composites | |
| CN111821982B (en) | Graphene oxide-cerium oxide-ferric oxide composite material, synthetic method and application thereof in catalytic degradability | |
| CN109621974B (en) | CuMn2O4Method for treating polluted water by ozone catalytic oxidation and removal of pollutants through rGO composite material | |
| CN113731430B (en) | Double Z-type CuO/CuBi 2 O 4 /Bi 2 O 3 Composite photocatalyst, preparation method and application thereof | |
| Rahman et al. | Superior photodegradation and antibacterial activity of r-GO supported ternary nanocomposite of doped transition metal compounds | |
| CN102357360A (en) | Catalyst for degrading rhodamine B by photocatalysis, and preparation method thereof | |
| CN112916045A (en) | Load ZnO-TiO2Preparation method of magnetic graphene oxide/chitosan composite material | |
| CN110227477B (en) | Preparation method and application of cobalt-doped bismuth ferrite compound three-phase composite catalyst | |
| CN108927172B (en) | Preparation and application of gold nanoparticle-loaded magnetic biomass carbon material | |
| Gul et al. | Photodegradation of orange II dye using pn junction NiO/TiO2 composite, and assessment of its biological activities | |
| Wang et al. | Preparation of non-polluting Tb-doped mesoporous carbon nitride photocatalyst and study on the efficacy and mechanism of degradation of antibiotics in water | |
| Santhosh et al. | Application of non-hierarchical gadolinium ortho-ferrite nanostructure for LED-driven photocatalytic mineralization of doxycycline hydrochloride | |
| Sharma et al. | Carbon quantum dots embedded trimetallic oxide: Characterization and photocatalytic degradation of Ofloxacin | |
| CN109772380B (en) | Hydrogenated titanium dioxide composite three-dimensional flower ball bismuth oxychloride photocatalyst and preparation method thereof | |
| CN114950520A (en) | CeO (CeO) 2 Doped with Na, K g-C 3 N 4 Fenton-like catalytic material and preparation method and application thereof | |
| CN102451682A (en) | Zirconia-modified wet oxidation catalyst and preparation method thereof | |
| CN111229200A (en) | Bismuth oxide modified Ti3+Self-doping TiO2Preparation method of heterojunction photocatalyst | |
| CN108097273B (en) | AgCl/BiOCl photocatalyst with tubular AgCl structure | |
| CN115739103A (en) | Visible light photocatalytic material CuO x @BiVO 4 And preparation method and application thereof | |
| CN110586146A (en) | Black titanium dioxide/silver phosphate composite photocatalyst and preparation method and application thereof | |
| CN111569890B (en) | Graphene oxide-terbium oxide-ferric oxide composite material, synthetic method and application thereof in catalytic degradation | |
| CN113244929A (en) | Iron bismuth oxide Bi2Fe4O9Preparation method and application in organic wastewater treatment | |
| CN110586139A (en) | Fe (III) cluster/bismuth oxyiodate composite photocatalytic material and preparation method and application thereof | |
| CN115555025B (en) | Preparation method of high-dispersion cobalt-molybdenum bimetallic catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |