CN110961129A - Reductive carbon nitride photocatalyst and preparation method and application thereof - Google Patents
Reductive carbon nitride photocatalyst and preparation method and application thereof Download PDFInfo
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- 230000002829 reductive effect Effects 0.000 title claims abstract description 31
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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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
- 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
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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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
- C02F2101/00—Nature of the contaminant
- 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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- 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 belongs to the technical field of photocatalysis, and discloses a reductive carbon nitride photocatalyst as well as a preparation method and application thereof. The photocatalyst is prepared by heating melamine to 520-550 ℃, roasting and grinding to obtain g-C3N4Powder; reacting NaBH4And g-C3N4Mixing the powder, and heating to 570-600 ℃ under a protective atmosphere; after cooling, the product is washed by deionized water and ethanol and dried to obtain the catalyst. The reductive carbon nitride catalyst disclosed by the invention does not contain metal, and has the advantages of environmental friendliness, stability, low cost and the like. The invention applies the reductive carbon nitride to the photocatalytic degradation of the diclofenac sodium for the first time, shows excellent photocatalytic performance and has good stability.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to a reductive carbon nitride photocatalyst as well as a preparation method and application thereof.
Background
In recent years, Pharmaceutical and Personal Care Products (PPCPs), which are new pollutants including various antibiotics, synthetic musk, analgesics, hypotensive drugs, contraceptives, hypnotics, weight loss drugs, hair sprays, hair dyes, bactericides, and the like, have received much attention. PPCPs have persistence and bioaccumulation properties and are difficult to degrade effectively by conventional biological processes, making them frequently detected in environmental aquatic environments. Residual PPCPs contaminants pose a potential threat to water quality and overall health of the ecosystem. Therefore, research and development of the efficient PPCPs treatment method have important significance for guaranteeing water quality safety and protecting ecological environment.
Semiconductor photocatalysis is considered to be an effective method for solving the problems of energy crisis and environmental pollution. Graphitic carbon nitride (g-C)3N4) As a metal-free organic polymer semiconductor, it is widely used because of its non-toxicity. However, due to the narrow visible light response range, the recombination rate of photogenerated electron-hole pairs is high and the oxidation activity is poor, g-C3N4Is limited in photocatalytic activity. To increase g-C3N4Various strategies have been tried, including metal or non-metal doping, semiconductor coupling, and morphology control, among others. Most strategies involve complex synthetic steps. Recently, a simple self-modification strategy has produced g-C with nitrogen vacancies3N4Effectively improves the photocatalytic activity.
Nitrogen Vacancies (NVs) not only enhance visibilityThe absorption of light can also inhibit the recombination of photo-generated electron-hole pairs. The nitrogen vacancy can be formed at g-C3N4Introduces additional energy levels to narrow the band gap and thereby enhance the absorption of visible light. Despite these advantages, a reduction in the band gap typically results in a downward shift in the Conduction Band (CB) and/or an upward shift in the Valence Band (VB), inevitably at the expense of the redox capability of the photocatalyst. Thus, adjusting g-C3N4The valence band is reduced and the VB position is lowered to improve the oxidation performance of the electron band structure, and for g-C3N4Efficient removal of organic contaminants is of paramount importance.
Disclosure of Invention
To address the above-discussed deficiencies and drawbacks of the prior art, it is an object of the present invention to provide a Reductive Carbon Nitride (RCN) photocatalyst. The composite photocatalyst introduces nitrogen vacancy and cyano (C ≡ N) to have low recombination rate of photo-generated electron-hole pairs and excellent visible light absorption and oxidation capacity, and can efficiently degrade diclofenac sodium in water under the irradiation of visible light.
The invention also aims to provide a preparation method of the carbon nitride photocatalyst based on the reductive graphite.
The invention further aims to provide application of the reductive graphite carbon nitride photocatalyst.
The purpose of the invention is realized by the following technical scheme:
a reductive carbon nitride photocatalyst is prepared by heating melamine to 520-550 ℃, roasting, and grinding to obtain g-C3N4Powder; reacting NaBH4And g-C3N4Mixing the powder, and heating to 570-600 ℃ under a protective atmosphere; cooling, washing and drying the product to obtain the product.
Preferably, the NaBH4And g-C3N4The mass ratio of the powder is (0.01-0.11): 1.
preferably, the protective atmosphere is nitrogen or argon.
Preferably, the roasting time is 4-5 h.
Preferably, the heating rate is 4-6 ℃/min, and the heating time is 20-40 min.
Preferably, the drying temperature is 65-75 ℃, and the drying time is 18-24 h.
Preferably, the cleaning reagent is deionized water and ethanol.
Preferably, the number of times of cleaning is 3-5 times.
The preparation method of the reductive carbon nitride photocatalyst comprises the following specific steps:
s1, heating melamine to 520-550 ℃, roasting, and grinding to obtain g-C3N4Powder;
s2, adding NaBH4And g-C3N4Mixing the powder, and heating to 570-600 ℃ under a protective atmosphere; and after cooling, washing the product with deionized water and ethanol, and drying to obtain the reducing carbon nitride photocatalyst.
The reductive carbon nitride photocatalyst is applied to degradation of diclofenac sodium under visible light.
The invention can reduce the positions of a Conduction Band (CB) and a Valence Band (VB) simultaneously and improve the oxidation capability of VB due to the introduction of electron-deficient groups (such as C ≡ N). According to the advantages of nitrogen vacancy and cyano (C ≡ N), the coexistence of nitrogen vacancy and C ≡ N can enhance the absorption of visible light, inhibit the recombination of photo-generated electron-hole pairs, and improve the oxidation capability, thereby improving the g-C ≡ N3N4Photocatalytic activity of (1).
Compared with the prior art, the invention has the following beneficial effects:
1. the invention successfully synthesizes the Reductive Carbon Nitride (RCN) with nitrogen vacancy and C [ identical to ] N functional group, reduces the band gap width, enhances the absorption of visible light and simultaneously improves the separation of photo-generated electron-hole pairs.
2. The Reductive Carbon Nitride (RCN) catalyst of the invention reduces the band gap width, shifts down the Valence Band (VB) position, improves the oxidation capability and enables the cavity (h)+) The hydroxyl radical (. OH) having a strong oxidizing property can be directly generated.
3. The RCN catalyst synthesized by the method is a metal-free polymer catalyst, and has the advantages of environmental protection, stability, low cost and the like.
4. The RCN is applied to photocatalytic degradation and degradation of diclofenac sodium for the first time, and the diclofenac sodium degrading agent shows excellent photocatalytic performance and has good stability.
5. The synthesis process is simple and has the basic conditions of practical application.
Drawings
FIG. 1 shows the Reducing Carbon Nitride (RCN) in example 1 and g-C in comparative example 13N4TEM images of transmission electron microscopy.
FIG. 2 shows RCN in example 1 and g-C in comparative example 13N4Room temperature electron paramagnetic resonance spectrum.
FIG. 3 is a graph of RCN in example 1 and g-C in comparative example 13N4Fourier transform infrared FTIR spectrum.
FIG. 4 is a graph of RCN in example 1 and g-C in comparative example 13N4Fluorescence spectrum of (2).
FIG. 5 is a graph of RCN in example 1 and g-C in comparative example 13N4Ultraviolet-visible diffuse reflectance DRS plot.
FIG. 6 is a graph of RCN in example 1 and g-C in comparative example 13N4Mott schottky curve of (a).
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
1. 5g of melamine were weighed into an alumina crucible and heated in a muffle furnace at 5 ℃ min-1Heating to 550 ℃ at the heating rate of (1) and keeping the temperature for 4 h. After it has cooled to room temperature, g-C is obtained by grinding and sieving3N4Powder;
2. mixing the components in a mass ratio of 0.05: 1 NaBH4And g-C3N4The powders were placed in a mortar and mixed thoroughly.
3. The well mixed sample was placed in a tube furnace at N2At 5 ℃ for min under atmosphere-1The temperature is increased to 600 ℃ at the rate of (1) and heated for 30 min.
4. After cooling in an open atmosphere, the product was rinsed 5 times with deionized water and ethanol and dried at 70 ℃ for 24h to produce a Reduced Carbon Nitride (RCN) photocatalyst powder.
FIG. 1 shows the Reducing Carbon Nitride (RCN) in the present example and g-C in comparative example 13N4Transmission Electron Microscopy (TEM) images of (a). Wherein (a) is g-C3N4And (b) is RCN. From FIG. 1, RCN and g-C can be found3N4All have a layered structure, but the surface of the RCN has an irregular porous structure. FIG. 2 shows RCN in the present example and g-C in comparative example 13N4Room temperature electron paramagnetic resonance spectrum. From FIG. 2, it can be seen that3N4In contrast, the paramagnetic signal of RCN was significantly enhanced, confirming that the RCN framework forms a defect. FIG. 3 shows RCN in the present example and g-C in comparative example 13N4Fourier transform infrared FTIR spectrum. From FIG. 3, it can be found that RCN is at 2180cm-1A new vibrational band, belonging to the cyano group (C.ident.N), was present, confirming the formation of C.ident.N in RCN. FIG. 4 shows RCN in the present example and g-C in comparative example 13N4Fluorescence spectrum of (2). From FIG. 4, it can be seen that the fluorescence intensity of RCN is significantly reduced, confirming that RCN enables efficient separation of photo-generated electron-hole pairs. FIG. 5 shows RCN in the present example and g-C in comparative example 13N4Ultraviolet-visible diffuse reflectance DRS plot. From fig. 5, it can be seen that the absorption edge of RCN undergoes a significant red shift, widening from 470nm to 500nm and the band gap decreases from 2.50eV to 2.36eV, confirming that the modified RCN enhances the absorption of visible light. FIG. 6 shows RCN in the present example and g-C in comparative example 13N4Mott schottky curve of (a). As can be seen from FIG. 6, the potentials are-0.56 and-0.95 eV (Ag/AgCl electrode), respectively, and the conduction band potentials are-0.34 eV and-0.71 eV, respectively, calculated by subtracting 0.24eV, respectively, and the combined band gap can beThe valence band potentials are 2.02eV and 1.79eV respectively, and the valence band of RCN is greater than OH/OH-Standard redox potential (+1.99eV), confirming the h of RCN+OH can be directly generated.
Application example 1
The application of Reductive Carbon Nitride (RCN) in degrading diclofenac sodium under visible light comprises the following steps:
1. 1 mg. L was added to the photolysis tube-1The RCN photocatalyst prepared in example 1 was prepared in the form of a diclofenac sodium solution at a concentration of 4mg/L in an amount of 50 ml.
2. And placing the prepared solution in a photochemical reactor for dark reaction for 30min, and then carrying out photocatalytic reaction to ensure that the catalyst and the DCF reach adsorption-desorption balance. The reaction time is 180min, and the residual concentration C of the diclofenac sodium in the solution is measured by a high performance liquid chromatograph after the reaction is finished.
3. Calculating the removal rate N of diclofenac sodium by the RCN photocatalyst, wherein the formula N is (C)0-C)/C0100% of C0The initial concentration of the diclofenac sodium and the C of the diclofenac sodium are the residual concentration, and the removal rate reaches 96.5 percent.
4. Photolytic modification of the g-C prepared in comparative example 1 into the tube3N4Repeating the steps 1-3 to calculate g-C3N4The removal rate of diclofenac sodium is 36.9%.
Comparative example 1
5g of melamine were weighed into an alumina crucible and heated in a muffle furnace at 5 ℃ min-1The heating rate of (3) was heated to 550 ℃ for 4 hours. After it is cooled to room temperature, g-C is prepared by grinding and sieving3N4A photocatalyst.
Table 1 removal rate of diclofenac sodium catalytically degraded by catalysts of example 1 and comparative example 1 under visible light irradiation for 180min
Table 1 shows the removal rate of diclofenac sodium catalytically degraded by the catalysts of example 1 and comparative example 1 under visible light irradiation for 180 min. Slave watch1, it can be seen that the removal rate of RCN is significantly higher than that of g-C in the same time period3N4Shows that the photocatalytic activity of RCN is better than that of g-C3N4。
Example 2
1. 5g of melamine were weighed into an alumina crucible and heated in a muffle furnace at 5 ℃ min-1Heating to 520 ℃ at the heating rate of (1) and keeping the temperature for 5 h. After it has cooled to room temperature, g-C is obtained by grinding and sieving3N4And (3) powder.
2. Mixing the components in a mass ratio of 0.11: 1 NaBH4And g-C3N4Mixing well in mortar, putting well-mixed sample into tube furnace, and adding N2At 6 ℃ min under atmosphere-1The temperature is increased to 570 ℃ at the rate of (1) and heated for 40 min.
3. After cooling in an open atmosphere, the product was rinsed 4 times with deionized water and ethanol and dried at 75 ℃ for 22h to produce a Reduced Carbon Nitride (RCN) photocatalyst powder.
Example 3
1. 5g of melamine were weighed into an alumina crucible and heated in a muffle furnace at 5 ℃ min-1Heating to 530 ℃ at the heating rate of (1) and keeping the temperature for 4.5 h. After it has cooled to room temperature, g-C is obtained by grinding and sieving3N4And (3) powder.
2. Mixing the components in a mass ratio of 0.08: 1 NaBH4And g-C3N4Mixing in a mortar, placing the mixed sample in a tube furnace, and heating at 6 deg.C/min under argon atmosphere-1The temperature is increased to 580 ℃ at the rate of (1) and heated for 35 min.
3. After cooling in an open atmosphere, the product was rinsed 3 times with deionized water and ethanol and dried at 65 ℃ for 20h to produce a Reduced Carbon Nitride (RCN) photocatalyst powder.
Example 4
1. 5g of melamine were weighed into an alumina crucible and heated in a muffle furnace at 5 ℃ min-1Heating to 530 ℃ at the heating rate of (1) and keeping the temperature for 4.5 h. After it has cooled to room temperature, g-C is obtained by grinding and sieving3N4And (3) powder.
2. Mixing the components in a mass ratio of 0.01:1 NaBH4And g-C3N4Mixing in a mortar, placing the mixed sample in a tube furnace, and heating at 6 deg.C/min under argon atmosphere-1The temperature is increased to 590 ℃ at the rate of (1) and heated for 35 min.
3. After cooling in an open atmosphere, the product was rinsed 4 times with deionized water and ethanol and dried at 70 ℃ for 18h to produce a Reduced Carbon Nitride (RCN) photocatalyst powder.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The reductive carbon nitride photocatalyst is characterized in that melamine is heated to 520-550 ℃, roasted and ground to obtain g-C3N4Powder; reacting NaBH4And g-C3N4Mixing the powder, and heating to 570-600 ℃ under a protective atmosphere; cooling, washing and drying the product to obtain the product.
2. The reductive carbon nitride photocatalyst as set forth in claim 1, wherein said NaBH is4And g-C3N4The mass ratio of the powder is (0.01-0.11): 1.
3. the reductive carbon nitride photocatalyst as set forth in claim 1, wherein the protective atmosphere is nitrogen or argon.
4. The reductive carbon nitride photocatalyst as set forth in claim 1, wherein the calcination time is 4-5 hours.
5. The reductive carbon nitride photocatalyst as set forth in claim 1, wherein the heating rate is 4-6 ℃/min and the heating time is 20-40 min.
6. The reductive carbon nitride photocatalyst as set forth in claim 1, wherein the drying temperature is 65-75 ℃ and the drying time is 18-24 hours.
7. The reductive carbon nitride photocatalyst as set forth in claim 1, wherein the cleaning reagents are deionized water and ethanol.
8. The reductive carbon nitride photocatalyst as set forth in claim 1, wherein the number of washing is 3 to 5.
9. A method for preparing a reductive carbon nitride photocatalyst as claimed in any one of claims 1 to 8, comprising the specific steps of:
s1, heating melamine to 520-550 ℃, roasting, and grinding to obtain g-C3N4Powder;
s2, adding NaBH4And g-C3N4Mixing the powder, and heating to 570-600 ℃ under a protective atmosphere; and after cooling, washing the product with deionized water and ethanol, and drying to obtain the reducing carbon nitride photocatalyst.
10. Use of the reductive carbon nitride photocatalyst of any one of claims 1-8 for degrading diclofenac sodium under visible light.
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| CN113318764A (en) * | 2021-05-28 | 2021-08-31 | 江苏大学 | Preparation method and application of nitrogen defect/boron doped tubular carbon nitride photocatalyst |
| CN113477269A (en) * | 2021-07-02 | 2021-10-08 | 中国科学技术大学 | Continuous regulation and control method of carbon nitride energy band structure and method for preparing hydrogen peroxide through photocatalysis |
| CN113908873A (en) * | 2021-09-18 | 2022-01-11 | 南开大学 | Method for selective oxidation of glucose by photocatalysis with carbon nitride based photocatalyst |
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| CN107744824A (en) * | 2017-04-19 | 2018-03-02 | 华中科技大学 | A kind of g C of modification3N4Base visible-light photocatalyst, its preparation method and application |
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| CN113318764A (en) * | 2021-05-28 | 2021-08-31 | 江苏大学 | Preparation method and application of nitrogen defect/boron doped tubular carbon nitride photocatalyst |
| CN113477269A (en) * | 2021-07-02 | 2021-10-08 | 中国科学技术大学 | Continuous regulation and control method of carbon nitride energy band structure and method for preparing hydrogen peroxide through photocatalysis |
| CN113477269B (en) * | 2021-07-02 | 2023-03-14 | 中国科学技术大学 | Continuous regulation and control method of carbon nitride energy band structure and method for preparing hydrogen peroxide through photocatalysis |
| CN113908873A (en) * | 2021-09-18 | 2022-01-11 | 南开大学 | Method for selective oxidation of glucose by photocatalysis with carbon nitride based photocatalyst |
| CN113908873B (en) * | 2021-09-18 | 2023-06-20 | 南开大学 | Method for selectively oxidizing glucose by photocatalysis of carbon nitride-based photocatalyst |
| CN115025804A (en) * | 2022-06-30 | 2022-09-09 | 哈尔滨工程大学 | Photocatalytic uranium-captured two-dimensional flaky semiconductor and preparation method thereof |
| CN115025804B (en) * | 2022-06-30 | 2023-01-31 | 哈尔滨工程大学 | Photocatalytic uranium-captured two-dimensional flaky semiconductor and preparation method thereof |
| CN116273129A (en) * | 2023-03-31 | 2023-06-23 | 重庆大学 | Nitrogen-containing vacancy carbon nitride material and preparation method and application thereof |
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