Mesoporous carbon composite material, preparation method and application thereof

Abstract

The present application relates to a kind of mesoporous carbon composite material and its preparation method and application.Mesoporous carbon composite material includes nitrogen-doped hollow mesoporous carbon and metal monatomic atom loaded on the nitrogen-doped hollow mesoporous carbon.The present application also provides the preparation method of mesoporous carbon composite material, including: adding 3-amino phenol and formaldehyde into alkali water, then adding the mixed solution of organic solvent and alkali, then adding cetyltrimethylammonium bromide, ethyl silicate and N, N-dimethylformamide in sequence, the product is calcined in nitrogen atmosphere, then mixed with the mixed solution of copper acetylacetonate and organic solvent, add in acetone solution, after ultrasonic heating reaction, calcined in nitrogen atmosphere, obtain mesoporous carbon composite material.The present application also provides the application of mesoporous carbon composite material as catalyst.The present application solves the problem of low degradation efficiency of existing catalyst, also solves the problem of large amount of existing catalyst.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of catalytic materials, in particular to a mesoporous carbon composite material and a preparation method and application thereof. BACKGROUND

[0002] In recent years, antibiotics have been widely used in human health care, livestock production and aquaculture, etc. However, the metabolism of animals to antibiotics is not complete, resulting in a large amount of unmetabolized antibiotics entering the environment with excrement and retaining their biological activity. These antibiotics entering environmental media such as water bodies and soils will force the production and spread of antibiotic resistance genes (ARGs) in bacterial communities. The widespread spread of ARGs may lead to the emergence of super-resistant bacteria, thereby posing a great threat to public health. In addition, the accumulation of antibiotics in the water environment will inhibit the growth and development of aquatic organisms, and may ultimately affect human health through the bioaccumulation of the food chain. In view of its potential harm, antibiotics have been listed in the list of key control new pollutants, and its treatment and control have become a major problem to be solved by scientific researchers.

[0003] As an emerging environmental remediation technology, advanced oxidation processes (AOPs) can effectively mineralize most pollutants by generating strong oxidizing free radicals to degrade organic pollutants, and decompose them into harmless substances such as carbon dioxide, water and inorganic salts. However, the free radicals (such as hydroxyl radicals and sulfate radicals) generated in the advanced oxidation process have an ultra-short lifetime (10 -6 ~10 -9 s), which greatly hinders the full contact and reaction of free radicals with organic pollutants, thereby limiting its application effect in heterogeneous reactions. In addition, the existing catalysts for activating persulfate to degrade antibiotics have problems such as large dosage and low degradation efficiency, which further restricts their application in actual environmental governance. Therefore, developing a new type of catalyst that can efficiently activate persulfate, improve the utilization rate of free radicals and has high degradation efficiency has important practical significance for solving the problem of antibiotic pollution. SUMMARY

[0004] Therefore, the purpose of the present application is to provide a mesoporous carbon composite material and a preparation method and application thereof, so as to solve the problem of low degradation efficiency of existing catalysts, and also solve the problem of large dosage of existing catalysts.

[0005] In order to achieve the above-mentioned purpose, the technical solutions adopted by the present application are as follows:

[0006] A mesoporous carbon composite material comprises nitrogen-doped hollow mesoporous carbon and metal monatomic atoms supported on the nitrogen-doped hollow mesoporous carbon.

[0007] According to the above technical means, by supporting metal monatomic atoms on nitrogen-doped hollow mesoporous carbon as a carrier, because the specific surface area of the nitrogen-doped hollow mesoporous carbon is large and the defect sites are increased, the loading amount and stability of copper monatomic atoms can be improved, so that when it is used as a catalyst, the ability of the material to activate persulfate can be enhanced, and then the antibiotics in the wastewater can be efficiently degraded. The problem of low degradation efficiency of the existing catalyst is solved, and the problem of large amount of the existing catalyst is also solved.

[0008] Preferably, the metal monatomic atoms are copper monatomic atoms.

[0009] The application also provides a preparation method of the mesoporous carbon composite material, comprising the following steps:

[0010] S1, adding 3-amino phenol and formaldehyde to alkaline water, reacting to obtain a first product;

[0011] S2, adding the first product to a mixed solution of an organic solvent and a base, then sequentially adding cetyltrimethylammonium bromide and ethyl silicate, mixing uniformly, then adding N,N-dimethylformamide, centrifuging, drying to obtain a solid product;

[0012] S3, calcining the solid product in a nitrogen atmosphere to obtain nitrogen-doped hollow mesoporous carbon;

[0013] S4, adding a mixed solution of acetylacetone copper and an organic solvent, and the nitrogen-doped hollow mesoporous carbon to a solution of acetone to obtain a first mixed solution;

[0014] S5, ultrasonically treating and then heating the first mixed solution to obtain a second product;

[0015] S6, heating the second product to a preset temperature in a nitrogen atmosphere, and calcining at constant temperature to obtain a mesoporous carbon composite material in the form of Cu-N3, that is, nitrogen-doped hollow mesoporous carbon loaded with metal monatomic atoms (N-HCMS@Cu-SACS).

[0016] The first product is formed by condensation reaction in an alkaline environment by using 3-amino phenol and formaldehyde as precursors, and then further reacted by a mixed solution of organic solvent and base to introduce hexadecyl trimethyl ammonium bromide and ethyl silicate to form a nitrogen-doped mesoporous carbon precursor with hollow structure. The structure and performance of the material are further optimized by calcination under nitrogen atmosphere. The uniform loading of copper monatomic is realized by the composite reaction of copper acetylacetonate and nitrogen-doped hollow mesoporous carbon. This structure not only increases the number of active sites of the catalyst, but also enhances the mass transfer efficiency and reaction activity through nitrogen doping and hollow mesoporous structure. Nitrogen doping provides more active sites, hollow mesoporous structure increases the specific surface area and mass transfer efficiency, and the uniform dispersion of copper monatomic further improves the catalytic efficiency. Therefore, the mesoporous carbon composite material of the present application exhibits higher degradation efficiency and lower catalyst dosage in the catalytic degradation reaction.

[0017] Preferably, the base is selected from aqueous ammonia.

[0018] Preferably, the organic solvent is selected from anhydrous ethanol.

[0019] Preferably, the volume ratio of base to water in the base water is 0.1-0.3:20-30.

[0020] Preferably, the water is deionized water and / or ultrapure water.

[0021] Preferably, the 3-amino phenol, the formaldehyde, the hexadecyl trimethyl ammonium bromide, the ethyl silicate and the N,N-dimethylformamide are 0.1-0.3 g:0.1-0.15 mL:0.1-0.3 g:5-10 mL:30-50 mL by g:mL:g:mL:mL.

[0022] Preferably, the volume ratio of organic solvent to base in the mixed solution of organic solvent and base is 20-30:0.5-1.5.

[0023] Preferably, the mass ratio of copper acetylacetonate to the nitrogen-doped hollow mesoporous carbon is 0.15-0.6:0.1-0.4.

[0024] Preferably, the calcination temperature in a nitrogen atmosphere is 550-800 ℃, and the time is 2-5 h.

[0025] Preferably, the preset temperature is 600-800 ℃, the time of constant temperature calcination is 3-6 h, the heating mode in a nitrogen atmosphere is programmed heating, and the heating rate of the programmed heating is 5 ℃ / min.

[0026] Preferably, the ultrasonic time is 4 h, the heating reaction temperature is 60-80 ℃, and the time is 6-8 h.

[0027] The application further provides application of the mesoporous carbon composite material prepared by the preparation method of the application as a catalyst.

[0028] Preferably, the mesoporous carbon composite material is used as a catalyst for catalyzing degradation of antibiotics in wastewater.

[0029] Preferably, the mesoporous carbon composite material is used as a catalyst for catalyzing degradation of antibiotics in wastewater by persulfate.

[0030] Preferably, the persulfate is selected from sodium persulfate.

[0031] Preferably, the antibiotics include at least one of tetracycline, oxytetracycline hydrochloride and sulfamethoxazole.

[0032] Preferably, the mass ratio of the persulfate to the mesoporous carbon composite material is 1:0.5-1.5.

[0033] Preferably, when the mass ratio of the antibiotics, the persulfate (PDS) and the mesoporous carbon composite material in the wastewater is 0.04-0.2:1:0.5-1.5, the time for reducing the antibiotics in the wastewater to 0 is 12-20 min.

[0034] Preferably, the method for catalyzing degradation of antibiotics in wastewater by the mesoporous carbon composite material as a catalyst comprises the following steps:

[0035] The persulfate and the mesoporous carbon composite material are added into wastewater containing antibiotics, mixed uniformly, and then reacted under normal temperature and pressure and in the dark to remove the antibiotics in the wastewater.

[0036] The mesoporous carbon composite material as a catalyst for catalyzing degradation of antibiotics in wastewater by the application directly adds the mesoporous carbon composite material and the persulfate into wastewater containing antibiotics, mixes uniformly, and then reacts under normal temperature and pressure and in the dark to remove the antibiotics in the wastewater, which not only avoids the complicated operation of the traditional persulfate catalyst which needs to be irradiated by ultraviolet light to realize catalysis, but also greatly improves the removal efficiency.

[0037] The application has the following beneficial effects:

[0038] The mesoporous carbon composite material of the application effectively improves the stability of the catalyst by ingeniously using nitrogen-doped hollow mesoporous carbon to load copper monatomic atoms, so that the degradation efficiency of the catalyst is improved and the use amount of the catalyst is reduced.

[0039] The preparation method of the mesoporous carbon composite material of the application, by using 3-amino phenol and formaldehyde as precursors, condensation reaction in alkaline environment to form a first product, and then further reaction by mixed solution of organic solvent and alkali, to introduce hexadecyl trimethyl ammonium bromide and ethyl silicate, to form a nitrogen-doped mesoporous carbon precursor with hollow structure. By calcination under nitrogen atmosphere, the structure and performance of the material are further optimized. By composite reaction of copper acetylacetone and nitrogen-doped hollow mesoporous carbon, uniform loading of copper single atoms is realized.

[0040] The mesoporous carbon composite material of the application is used as a catalyst for catalyzing persulfate to degrade antibiotics in wastewater, and the catalyst shows excellent performance in removing tetracycline by activating PDS, with a removal rate of 83% in 4 minutes and complete degradation in 8 minutes. In the field of catalytic materials and antibiotic wastewater treatment technology, it has application value. BRIEF DESCRIPTION OF DRAWINGS

[0041] Figure 1 The degradation test result graph of antibiotic TC in wastewater;

[0042] Figure 2 The degradation test result graph of antibiotic TC in wastewater with different catalyst dosages;

[0043] Figure 3 The degradation test result graph of antibiotic TC in wastewater with different TC initial concentrations;

[0044] Figure 4 The degradation test result graph of antibiotic TC in wastewater with different pH values;

[0045] Figure 5 The degradation test result graph of antibiotic TC in wastewater with catalyst recycling;

[0046] Figure 6 The degradation test result graph of antibiotic TC in wastewater with increased quencher;

[0047] Figure 7 The degradation test result graph of antibiotic TC in different water matrices;

[0048] Figure 8 The degradation test result graph of different antibiotic wastewater by the catalyst;

[0049] Figure 9 The SEM graph of N-HCMS and N-HCMS@Cu-SAC obtained in Example 1;

[0050] Figure 10 The XRD graph of N-HCMS@Cu-SAC obtained in Example 1;

[0051] Figure 11An HAADF-STEM image of the N-HCMS@Cu-SAC obtained in Example 1;

[0052] Figure 12 A graph of the EPR test results of the catalyst. DETAILED DESCRIPTION

[0053] Other advantages and embodiments of the present application will be disclosed in the following description of preferred embodiments with reference to the accompanying drawings. The present application can be implemented or applied in other different specific embodiments, and the details in the specification can be modified or changed based on different views and applications without departing from the spirit of the present application. It should be understood that the preferred embodiments are only for illustrating the present application, but not for limiting the protection scope of the present application.

[0054] The present application provides a mesoporous carbon composite material, a preparation method and application thereof, to solve the problem of low degradation efficiency of existing catalysts, and to solve the problem of large amount of existing catalysts, to improve the stability of metal single-atom catalysts, to reduce the leaching rate of metal ions, to enhance the ability to activate persulfate, and to maintain high catalytic performance in various environments.

[0055] The mesoporous carbon composite material comprises nitrogen-doped hollow mesoporous carbon and metal single atoms loaded on the nitrogen-doped hollow mesoporous carbon.

[0056] In some embodiments, the metal single atoms are copper single atoms.

[0057] In some embodiments, a preparation method of the mesoporous carbon composite material is also provided, comprising the following steps:

[0058] S1, adding 3-amino phenol and formaldehyde into alkaline water, reacting to obtain a first product;

[0059] S2, adding the first product into a mixed solution of an organic solvent and a base, then sequentially adding cetyltrimethylammonium bromide and ethyl silicate, mixing uniformly, then adding N,N-dimethylformamide, centrifuging, drying to obtain a solid product;

[0060] S3, calcining the solid product in a nitrogen atmosphere to obtain nitrogen-doped hollow mesoporous carbon;

[0061] S4, mixing a mixed solution of copper acetylacetonate and an organic solvent, nitrogen-doped hollow mesoporous carbon and water, then adding into a solution of acetone to obtain a first mixed solution;

[0062] S5, ultrasonicating the first mixed solution, then heating to react to obtain a second product;

[0063] S6, the second product is heated to a preset temperature in a nitrogen atmosphere, and constant temperature calcination is performed to obtain a Cu-N3 form mesoporous carbon composite material, i.e., a nitrogen-doped hollow mesoporous carbon (N-HCMS@Cu-SACS) loaded with metal monatomic atoms.

[0064] In some embodiments, the base is selected from aqueous ammonia.

[0065] In some embodiments, the organic solvent is selected from anhydrous ethanol.

[0066] In some embodiments, in the aqueous base, the volume ratio of the base to water is 0.1-0.3:20-30.

[0067] In some embodiments, the water is deionized water and / or ultrapure water.

[0068] In some embodiments, the 3-amino phenol, the formaldehyde, the cetyltrimethylammonium bromide, the ethyl silicate, and the N,N-dimethylformamide are 0.1-0.3 g:0.1-0.15 mL:0.1-0.3 g:5-10 mL:30-50 mL by g:mL:g:mL:mL.

[0069] In some embodiments, in the mixed solution of the organic solvent and the base, the volume ratio of the organic solvent to the base is 20-30:0.5-1.5.

[0070] In some embodiments, the mass ratio of the copper acetylacetonate to the nitrogen-doped hollow mesoporous carbon is 0.15-0.6:0.1-0.4.

[0071] In some embodiments, the temperature for calcination in a nitrogen atmosphere is 550-800 ℃, and the time is 2-5 h.

[0072] In some embodiments, the preset temperature is 600-800 ℃, the time for constant temperature calcination is 3-6 h, the heating mode in a nitrogen atmosphere is programmed heating, and the programmed heating rate is 5 ℃ / min.

[0073] In some embodiments, the time for ultrasonic is 4 h, the temperature for heating reaction is 60-80 ℃, and the time is 6-8 h.

[0074] In some embodiments, the mesoporous carbon composite material prepared by the preparation method is also provided as a catalyst.

[0075] In some embodiments, the mesoporous carbon composite material as a catalyst is used for catalyzing degradation of antibiotics in wastewater.

[0076] In some embodiments, the mesoporous carbon composite material as a catalyst is used for catalyzing degradation of antibiotics in wastewater by persulfate.

[0077] In some embodiments, the persulfate salt is selected from sodium persulfate;

[0078] In some embodiments, the antibiotic comprises at least one of tetracycline, oxytetracycline hydrochloride, and sulfamethoxazole.

[0079] In some embodiments, the mass ratio of the persulfate salt to the mesoporous carbon composite material is 1:0.5-1.5.

[0080] In some embodiments, when the mass ratio of the antibiotic, the persulfate salt (PDS), and the mesoporous carbon composite material in the sewage is 0.04-0.2:1:0.5-1.5, the time for reducing the antibiotic in the sewage to 0 is 12-20 min.

[0081] In some embodiments, the mesoporous carbon composite material is used as a catalyst in a method for catalyzing the persulfate salt to degrade the antibiotic in the sewage, comprising the following steps:

[0082] The persulfate salt and the mesoporous carbon composite material are added to the sewage containing the antibiotic, mixed uniformly, and then reacted under normal temperature and pressure and in the dark to remove the antibiotic in the sewage.

[0083] The mesoporous carbon composite material of the present application is used as a catalyst in a method for catalyzing the persulfate salt to degrade the antibiotic in the sewage, which directly adds the mesoporous carbon composite material and the persulfate salt to the sewage containing the antibiotic, mixes uniformly, and then reacts under normal temperature and pressure and in the dark to remove the antibiotic in the sewage, which not only avoids the cumbersome operation of the traditional persulfate salt catalyst which needs to be irradiated by ultraviolet light to realize the catalytic effect, but also greatly improves the removal efficiency.

[0084] In order to make the technical problems, technical solutions and beneficial effects solved by the present application clearer, the mesoporous carbon composite material, its preparation method and application will be further described in detail below in combination with specific embodiments and drawings. Obviously, the specific embodiments described are only some of the embodiments of the present application, not all. The following description of at least one exemplary embodiment is merely illustrative and in no way limits the present application and its applications. Based on the specific embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative labor fall within the scope of the present application.

[0085] Unless otherwise specified in the specific embodiments, the technology or conditions are carried out according to the technology or conditions described in the literature in the art or according to the product manual. Unless otherwise specified, the reagents or instruments used are conventional products that can be obtained from the market.

[0086] Example 1

[0087] A preparation method of a mesoporous carbon composite material, comprising the following steps:

[0088] S1, 0.1 mL of ammonia water is mixed with 30 mL of deionized water, stirred for more than 1 h, then 0.1 g of 3-aminophenol is added, continuously stirred for 30 min, then 0.14 mL of formaldehyde solution is added, stirred for 30 min at a temperature of 30°C, to obtain a first product;

[0089] S2, the first product prepared in S1 is added to a mixed solution of 50 mL of deionized water, 20 mL of anhydrous ethanol and 1 mL of ammonia water, stirred for 5 min, then 0.2 g of cetyltrimethylammonium bromide is added, and then 10 mL of ethyl silicate is added dropwise, mixed uniformly, reacted for 10 h, then 35 mL of N,N-dimethylformamide is added to dissolve the oligomer, the precipitated product is collected by centrifugation, and then the precipitated product is dried at a temperature of 60°C for 8 h to obtain a solid product;

[0090] S3, the solid product obtained in S2 is calcined at a temperature of 800°C for 3 h in a nitrogen (N2) atmosphere to realize carbonization and etching, to obtain nitrogen-doped hollow mesoporous carbon (i.e. N-HMCS);

[0091] S4, 0.3 g of copper acetylacetonate is added to 20 mL of anhydrous ethanol, then 0.2 g of nitrogen-doped hollow mesoporous carbon is added, and then 50 mL of acetone is added, stirred uniformly to obtain a first mixed solution;

[0092] S5, the first mixed solution obtained in S4 is ultrasonically treated for 4 h, and then reacted at a constant temperature in an oven at a temperature of 80°C for 8 h to obtain a second product;

[0093] S6, the second product is heated to 800°C at a heating rate of 5°C / min in a nitrogen atmosphere, and then calcined at a constant temperature at 800°C for 3 h in a nitrogen atmosphere to obtain a mesoporous carbon composite material in the form of Cu-N3, i.e. nitrogen-doped hollow mesoporous carbon loaded with metal monatomic atoms (N-HCMS@Cu-SACS).

[0094] Example 2

[0095] A preparation method of a mesoporous carbon composite material, comprising the following steps:

[0096] S1, 0.1 mL of ammonia water is mixed with 30 mL of deionized water, stirred for more than 1 h, then 0.1 g of 3-aminophenol is added, continuously stirred for 30 min, then 0.14 mL of formaldehyde solution is added, stirred for 30 min at a temperature of 30°C, to obtain a first product;

[0097] S2, adding the first product prepared in S1 to a mixed solution of 50 mL of deionized water, 20 mL of anhydrous ethanol and 1 mL of ammonia water, stirring for 5 min, then adding 0.2 g of cetyltrimethylammonium bromide, and then adding 10 mL of ethyl silicate dropwise, uniformly mixing and reacting for 10 h, then adding 35 mL of N,N-dimethylformamide to dissolve the oligomer, collecting the precipitated product by centrifugation, and then drying the precipitated product at a temperature of 60 ℃ for 8 h to obtain a solid product;

[0098] S3, calcining the solid product obtained in S2 under a nitrogen (N2) atmosphere at a temperature of 800 ℃ for 3 h to realize carbonization and etching, and obtaining nitrogen-doped hollow mesoporous carbon (N-HMCS);

[0099] S4, adding 0.6 g of copper acetylacetonate to 20 mL of anhydrous ethanol, then adding 0.2 g of nitrogen-doped hollow mesoporous carbon, and then adding 50 mL of acetone, and stirring to obtain a first mixed solution;

[0100] S5, ultrasonic treating the first mixed solution obtained in S4 for 4 h, and then reacting in an oven at a temperature of 80 ℃ for 8 h to obtain a second product;

[0101] S6, heating the second product from room temperature to 800 ℃ at a heating rate of 5 ℃ / min in a nitrogen atmosphere, and then calcining at a temperature of 800 ℃ for 3 h under a nitrogen atmosphere to obtain a Cu-N3 form mesoporous carbon composite material, i.e., a nitrogen-doped hollow mesoporous carbon (N-HCMS@Cu-SACS-1) loaded with a metal monatomic atom.

[0102] Example 3

[0103] A method for preparing a mesoporous carbon composite material, comprising the following steps:

[0104] S1, mixing 0.1 mL of ammonia water with 30 mL of deionized water, stirring for more than 1 h, then adding 0.1 g of 3-aminophenol, continuously stirring for 30 min, then adding 0.14 mL of formaldehyde solution, and stirring at a temperature of 30 ℃ for 30 min to obtain a first product;

[0105] S2, to the mixed solution of 50 mL deionized water, 20 mL anhydrous ethanol and 1 mL ammonia water, the first product prepared in S1 was added, stirred for 5 min, then 0.2 g of cetyltrimethylammonium bromide was added, and then 10 ml of ethyl silicate was added dropwise, and the mixture was uniformly reacted for 10 h, then 35 mL of N, N-dimethylformamide was added to dissolve the oligomer, the precipitated product was collected by centrifugation, and then the precipitated product was dried at a temperature of 60 ℃ for 8 h to obtain a solid product;

[0106] S3, the solid product obtained in S2 was calcined at a temperature of 800 ℃ for 3 h under a nitrogen (N2) atmosphere to realize carbonization and etching, and nitrogen-doped hollow mesoporous carbon (N-HMCS) was obtained;

[0107] S4, 0.3 g of copper acetylacetonate was added to 20 mL of anhydrous ethanol, then 0.4 g of nitrogen-doped hollow mesoporous carbon was added, and then 50 mL of acetone was added, and the mixture was stirred uniformly to obtain a first mixed solution;

[0108] S5, the first mixed solution obtained in S4 was ultrasonically treated for 4 h, and then reacted in an oven at a temperature of 80 ℃ for 8 h to obtain a second product;

[0109] S6, the second product was heated to 800 ℃ at a heating rate of 5 ℃ / min under a nitrogen atmosphere, and then calcined at a temperature of 800 ℃ for 3 h under a nitrogen atmosphere to obtain Cu-N3 form mesoporous carbon composite material, namely nitrogen-doped hollow mesoporous carbon loaded with metal monatomic (N-HCMS@Cu-SACS-2).

[0110] Example 4

[0111] The method for the nitrogen-doped hollow mesoporous carbon loaded with metal monatomic (N-HCMS@Cu-SACS) as a catalyst to catalyze sodium persulfate to degrade tetracycline (TC) in wastewater comprises the following steps:

[0112] The N-HCMS@Cu-SACS prepared in Example 1 was added to 40 mL of wastewater containing tetracycline, wherein the initial concentration of tetracycline in the wastewater was 10 mg / L, the pH value of the wastewater was adjusted to 6 with 0.1 M NaOH or 0.1 M H2SO4, and the reaction was stirred for 30 min to establish adsorption equilibrium, then 10 mg of sodium persulfate was added to form an N-HCMS@Cu-SACS / PDS system, and the catalytic reaction was started under normal temperature and pressure and in the dark. At 2 min, 4 min, 6 min, 8 min, 10 min and 12 min, 1 mL of the reacted liquid was collected by 0.22 μm polyethersulfone membrane filtration and detected on a high performance liquid chromatograph. The degradation of TC was determined with the original wastewater containing 10 mg / L of tetracycline as a control, and the results are shown in Figure 1 .

[0113] Example 5

[0114] The effect of catalyst dosage on the degradation efficiency of TC by N-HCMS@Cu-SACS / PDS was investigated.

[0115] A method for degrading tetracycline (TC) in wastewater by sodium persulfate using N-HCMS@Cu-SACS as a catalyst, comprising the following steps:

[0116] 5 mg, 10 mg, 15 mg and 20 mg of N-HCMS@Cu-SACS prepared in Example 1 were added to 40 mL of wastewater containing tetracycline, respectively, wherein the initial concentration of tetracycline in the wastewater was 10 mg / L, the pH value of the wastewater was adjusted to 6 with 0.1 M NaOH or 0.1 M H2SO4, and the reaction was stirred for 30 min to establish adsorption equilibrium, then 10 mg of sodium persulfate was added to form an N-HCMS@Cu-SACS / sodium persulfate system, and the catalytic reaction was started under normal temperature and pressure and in the dark. At 2 min, 4 min, 6 min, 8 min, 10 min and 12 min, 1 mL of the reacted liquid was collected by 0.22 μm polyethersulfone membrane filtration and detected on a high performance liquid chromatograph. The degradation of TC was determined with the original wastewater containing 10 mg / L of tetracycline as a control, and the results are shown in Figure 2 .

[0117] Example 6

[0118] The effect of TC initial concentration on the degradation efficiency of TC by N-HCMS@Cu-SACS / PDS was investigated.

[0119] A method for degrading tetracycline (TC) in wastewater by using nitrogen-doped hollow mesoporous carbon (N-HCMS@Cu-SACS) loaded with metal monatomic as catalyst to catalyze sodium persulfate, comprising the following steps:

[0120] 15 mg of N-HCMS@Cu-SACS prepared in Example 1 was added into 40 mL of wastewater containing tetracycline, wherein the initial concentration of tetracycline in the wastewater was 5 mg / L, 10 mg / L, 20 mg / L, 30 mg / L, and 50 mg / L, respectively, and the pH value of the wastewater was adjusted to 6 by using 0.1 M NaOH or 0.1 M H2SO4, and the reaction was stirred for 30 min to establish adsorption equilibrium, then 10 mg of sodium persulfate was added to form N-HCMS@Cu-SACS, sodium persulfate system, and the catalytic reaction was started under normal temperature and pressure and in the dark, 1 mL of the liquid after reaction was collected by filtering through a 0.22 μm polyethersulfone membrane at 2 min, 4 min, 6 min, 8 min, 10 min, and 12 min, and was detected on a high performance liquid chromatograph to determine the degradation of TC, and the results are shown in Figure 3 .

[0121] Example 7

[0122] The effect of wastewater pH on the degradation efficiency of TC by N-HCMS@Cu-SACS / PDS was investigated.

[0123] A method for degrading tetracycline (TC) in wastewater by using nitrogen-doped hollow mesoporous carbon (N-HCMS@Cu-SACS) loaded with metal monatomic as catalyst to catalyze sodium persulfate, comprising the following steps:

[0124] 15 mg of N-HCMS@Cu-SACS prepared in Example 1 was added into 40 mL of wastewater containing tetracycline, wherein the initial concentration of tetracycline in the wastewater was 10 mg / L, and the pH value of the wastewater was adjusted to 1, 3, 5, 6, 7, and 9, respectively, by using 0.1 M NaOH or 0.1 M H2SO4, and the reaction was stirred for 30 min to establish adsorption equilibrium, then 10 mg of sodium persulfate was added to form N-HCMS@Cu-SACS, sodium persulfate system, and the catalytic reaction was started under normal temperature and pressure and in the dark, 1 mL of the liquid after reaction was collected by filtering through a 0.22 μm polyethersulfone membrane at 2 min, 4 min, 6 min, 8 min, 10 min, and 12 min, and was detected on a high performance liquid chromatograph to determine the degradation of TC, and the results are shown in Figure 4 .

[0125] Example 8

[0126] The recyclability of the catalyst was evaluated, the catalyst after the reaction was collected by filtration and washed several times with deionized water and ethanol before use, and the above application example operation was continued to repeat 5 times.

[0127] A method for degrading tetracycline (TC) in wastewater by sodium persulfate using nitrogen-doped hollow mesoporous carbon (N-HCMS@Cu-SACS) loaded with metal monatomic as catalyst, comprising the following steps:

[0128] 15 mg of N-HCMS@Cu-SACS prepared in Example 1 was added to 40 mL of wastewater containing tetracycline, wherein the initial concentration of tetracycline in the wastewater was 10 mg / L, the pH value of the wastewater was adjusted to 6 with 0.1 M NaOH or 0.1 M H2SO4, and the reaction was stirred for 30 min to establish adsorption equilibrium, then 10 mg of sodium persulfate was added to form a N-HCMS@Cu-SACS, sodium persulfate system, and the catalytic reaction was started under normal temperature and pressure and in the dark. At 2 min, 4 min, 6 min, 8 min, 10 min and 12 min, 1 mL of the reaction liquid was collected by 0.22 μm polyether sulfone membrane filtration and detected by high performance liquid chromatography. The catalyst after the reaction was collected by filtration and washed several times with deionized water and ethanol before use, and the above operation was continued to repeat 5 times to determine the degradation of TC, and the results are shown in Figure 5

[0129] Example 9

[0130] Effect of quenching agent on TC degradation efficiency of N-HCMS@Cu-SACS / PDS

[0131] A method for degrading tetracycline (TC) in wastewater by sodium persulfate using nitrogen-doped hollow mesoporous carbon (N-HCMS@Cu-SACS) loaded with metal monatomic as catalyst, comprising the following steps:

[0132] ​The N-HCMS@Cu-SACS prepared in Example 1 was added to 40 mL of wastewater containing tetracycline, wherein the initial concentration of tetracycline in the wastewater was 10 mg / L, the pH value of the wastewater was adjusted to 6 with 0.1 M NaOH or 0.1 M H2SO4, and the reaction was stirred for 30 min to establish adsorption equilibrium, then 10 mg of sodium persulfate was added, and 100 mM methanol (MEOH), 100 mM tert-butyl alcohol (TBA), 100 mM furfuryl alcohol (FA), or 100 mM p-benzoquinone (PBQ) was added as a quenching agent, respectively, to form an N-HCMS@Cu-SACS, sodium persulfate system, and the catalytic reaction was started under normal temperature and pressure and in the dark. At 2 min, 4 min, 6 min, 8 min, 10 min, and 12 min of reaction, 1 mL of the reacted liquid was collected by 0.22 μm polyethersulfone membrane filtration, and detected on a high-performance liquid chromatograph to determine the degradation of TC, and the results are shown in Figure 6 .

[0133] Example 10

[0134] Exploring the degradation efficiency of TC in different water matrices

[0135] A method for degrading tetracycline (TC) in wastewater by sodium persulfate using nitrogen-doped hollow mesoporous carbon loaded with metal monatomic atoms (N-HCMS@Cu-SACS) as a catalyst, comprising the following steps:

[0136] The N-HCMS@Cu-SACS prepared in Example 1 was added to 40 mL of wastewater containing tetracycline, wherein the initial concentration of tetracycline in the wastewater was 10 mg / L, the pH value of the wastewater was adjusted to 6 with 0.1 M NaOH or 0.1 M H2SO4, and the reaction was stirred for 30 min to establish adsorption equilibrium, then 10 mg of sodium persulfate was added, and 100 mM methanol (MEOH), 100 mM tert-butyl alcohol (TBA), 100 mM furfuryl alcohol (FA), or 100 mM p-benzoquinone (PBQ) was added as a quenching agent, respectively, to form an N-HCMS@Cu-SACS, sodium persulfate system, and the catalytic reaction was started under normal temperature and pressure and in the dark. At 2 min, 4 min, 6 min, 8 min, 10 min, and 12 min of reaction, 1 mL of the reacted liquid was collected by 0.22 μm polyethersulfone membrane filtration, and detected on a high-performance liquid chromatograph to determine the degradation of TC, and the results are shown in Figure 7 .

[0137] Example 11

[0138] Exploring the degradation efficiency of the catalyst on different antibiotics

[0139] A method for degrading tetracycline (TC), oxytetracycline HCL and sulfamethoxazole (SMX) in wastewater by sodium persulfate catalyzed by metal atom-doped nitrogen-doped hollow mesoporous carbon (N-HCMS@Cu-SACS) as catalyst, comprising the following steps:

[0140] 15 mg of N-HCMS@Cu-SACS prepared in Example 1 was added into 40 mL of wastewater containing tetracycline, oxytetracycline HCL and sulfamethoxazole, wherein the initial concentration of tetracycline, oxytetracycline HCL and sulfamethoxazole in the wastewater was 10 mg / L, the pH value of the wastewater was adjusted to 6 by 0.1 M NaOH or 0.1 M H2SO4, and the reaction was stirred for 30 min to establish adsorption equilibrium, then 10 mg of sodium persulfate was added to form a N-HCMS@Cu-SACS, sodium persulfate system, and the catalytic reaction was started under normal temperature and pressure and in the dark, 1 mL of the reacted liquid was collected by 0.22 μm polyethersulfone membrane filtration at 2 min, 4 min, 6 min, 8 min, 10 min and 12 min, and detected on a high performance liquid chromatograph, the degradation of TC was determined by taking the wastewater containing 10 mg / L of tetracycline as a control, and the results are shown in Figure 8 .

[0141] Comparative Example 1

[0142] A method for degrading tetracycline (TC) in wastewater by sodium persulfate catalyzed by copper acetylacetonate as catalyst, comprising the following steps:

[0143] 15 mg of copper acetylacetonate was added into 40 mL of wastewater containing tetracycline, wherein the concentration of tetracycline in the wastewater was 10 mg / L, the pH value of the wastewater was adjusted to 6 by 0.1 M NaOH or 0.1 M H2SO4, and the reaction was stirred for 30 min to establish adsorption equilibrium, then 10 mg of sodium persulfate was added to form a Cu, sodium persulfate system, and the catalytic reaction was started under normal temperature and pressure and in the dark, 1 mL of the reacted liquid was collected by 0.22 μm polyethersulfone membrane filtration at 2 min, 4 min, 6 min, 8 min, 10 min and 12 min, and detected on a high performance liquid chromatograph, the degradation of TC was determined, and the results are shown in Figure 1 .

[0144] Comparative Example 2

[0145] A method for degrading tetracycline (TC) in wastewater by sodium persulfate catalyzed by nitrogen-doped hollow mesoporous carbon (N-HMCS) as catalyst, comprising the following steps:

[0146] 15 mg N-HMCS was added into 40 mL sewage containing tetracycline, wherein the concentration of tetracycline in the sewage was 10 mg / L, the pH value of the sewage was adjusted to 6 by 0.1 M NaOH or 0.1 M H2SO4, and the reaction was stirred for 30 min to establish adsorption equilibrium, then 10 mg sodium persulfate was added to form an N-HMCS-sodium persulfate system, and the catalytic reaction was started under normal temperature and pressure and in the dark, 1 mL of the reacted liquid was collected by 0.22 μm polyether sulfone membrane filtration at 2 min, 4 min, 6 min, 8 min, 10 min and 12 min, and detected on a high performance liquid chromatograph to determine the degradation of TC, and the results are shown in Figure 1 .

[0147] Comparative Example 3

[0148] The method for degrading tetracycline (TC) in sewage by only adding N-HCMS@Cu-SACS includes the following steps:

[0149] 15 mg N-HCMS@Cu-SACS was added into 40 mL sewage containing tetracycline, wherein the concentration of tetracycline in the sewage was 10 mg / L, the pH value of the sewage was adjusted to 6 by 0.1 M NaOH or 0.1 M H2SO4, and the reaction was stirred for 30 min to establish adsorption equilibrium, then 10 mg sodium persulfate was added to form an N-HMCS-sodium persulfate system, and the catalytic reaction was started under normal temperature and pressure and in the dark, 1 mL of the reacted liquid was collected by 0.22 μm polyether sulfone membrane filtration at 2 min, 4 min, 6 min, 8 min, 10 min and 12 min, and detected on a high performance liquid chromatograph to determine the degradation of TC, and the results are shown in Figure 1 .

[0150] Detection and analysis

[0151] 1) Characterization of N-HCMS and N-HCMS@Cu-SAC

[0152] The morphology, physical and chemical properties and catalytic activity of N-HCMS prepared in S3 of Example 1 and N-HCMS@Cu-SAC prepared in S6 of Example 1 were analyzed, detected and characterized. The morphology of the catalyst was observed by scanning electron microscope SEM. The phase of the catalyst was studied by X-ray diffraction XRD. The dispersion degree of copper single atoms was determined by spherical aberration electron microscopy-high angle annular dark field-scanning transmission electron microscopy HAADF-STEM. The results are shown in Figures 9 to 11 .

[0153] Figure 9SEM images of N-HCMS obtained in S3 and N-HCMS@Cu-SAC obtained in S6 of Example 1 are shown. Figure 9 It can be seen that N-HCMS has a hollow spherical structure, a large specific surface area, and a uniform pore size distribution. The specific surface area of ​​this composite material is 1140-1255 m². 2 g -1 N-HCMS@Cu-SAC is distributed in particulate form.

[0154] Figure 10 The image shows the XRD pattern of N-HCMS@Cu-SAC obtained in S6 of Example 1. From... Figure 10 It can be seen that the characteristic diffraction peak of the (002) crystal plane of graphitic carbon nitride appears at 27.5°; no specific peak of Cu nanoparticles was observed, proving that the anchored Cu has been converted into Cu single atoms in mesoporous carbon.

[0155] Figure 11 The image shows the HAADF-STEM image of N-HCMS@Cu-SAC obtained in S6 of Example 1. From... Figure 11 It can be seen that Cu is distributed on N-HCMS in the form of individual atoms, with the size of a single Cu atom being 0.26 nm.

[0156] Degradation analysis of antibiotics in wastewater

[0157] Figure 1 In this context, N-HCMS@Cu-SACS, PDS corresponds to the degradation system in Example 4; N-HMCS, PDS corresponds to the degradation system in Control Example 2; Cu, PDS corresponds to the degradation system in Control Example 1; N-HCMS@Cu-SACS corresponds to the degradation system in Control Example 3; and Blank corresponds to the wastewater containing 10 mg / L tetracycline. Figure 1 The results show that the N-HCMS@Cu-SACS / PDS system achieved a 100% degradation rate of TC after 4 minutes. The Cu / PDS system achieved a 24% degradation rate of TC, while the N-HCMS / PDS system achieved a 61% degradation rate. This demonstrates that N-HCMS@Cu-SACS can effectively degrade tetracycline with high efficiency.

[0158] From such Figure 2 and Figure 3 Analysis revealed that the optimal amounts of N-HCMS@Cu-SACS and TC concentrations during the reaction were 15 mg and 10 mg / L, respectively.

[0159] from Figure 4Analysis showed that within the pH range of 3 to 9, the degradation rate of TC by the N-HCMS@Cu-SACS / PDS system reached 100% with increasing time. When the pH was 1 and 11, the degradation rate of TC decreased slightly to 76.4% and 83.3%, respectively.

[0160] from Figure 5 Analysis showed that the catalyst used after a single recovery had no significant impact on the degradation efficiency of TC. However, when N-HCMS@Cu-SACS was recovered multiple times, the degradation efficiency of TC decreased significantly. This may be related to the byproducts remaining on the catalyst surface.

[0161] from Figure 6 Analysis shows that N-HCMS@Cu-SACS can activate PDS to produce ·OH and SO4. - ·, O2ˉ·, and 1 O2 and other active oxygen species remove tetracycline from water. 1 O2 contributes significantly. Figure 12 EPR testing detected ·OH and SO4. - ·, O2ˉ·, and 1 The O2 signal also confirms this conclusion.

[0162] from Figure 7 Analysis showed that in deionized water, tap water, and river water, the removal rates of TC after 12 min were 100%, 94.3%, and 81.6%, respectively. The N-HCMS@Cu-SACS / PDS system demonstrated good TC removal performance and a fast reaction rate.

[0163] from Figure 8 Analysis showed that in solutions containing tetracycline, oxytetracycline hydrochloride, and sulfamethoxazole, the removal rates of these pollutants after 12 minutes were 100%, 98.2%, and 99.1%, respectively. This demonstrates that the N-HCMS@Cu-SACS / PDS system has a highly efficient removal effect on antibiotics.

[0164] The above embodiments are merely preferred embodiments provided to fully illustrate the present invention, and the scope of protection of the present invention is not limited thereto. Equivalent substitutions or modifications made by those skilled in the art based on the present invention are all within the scope of protection of the present invention.

Claims

1. A method for producing a mesoporous carbon composite material, characterized by, The mesoporous carbon composite material comprises nitrogen-doped hollow mesoporous carbon and metal monatomic atoms loaded on the nitrogen-doped hollow mesoporous carbon; The metal monatomic atoms are copper monatomic atoms, and the mesoporous carbon composite material is a mesoporous carbon composite material in the form of Cu-N3; The mesoporous carbon composite material is used as a catalyst for catalyzing the degradation of antibiotics in wastewater by persulfate; The preparation method comprises the following steps: S1, adding 3-amino phenol and formaldehyde into alkaline water, reacting to obtain a first product; S2, adding the first product into a mixed solution of an organic solvent and a base, then sequentially adding hexadecyl trimethyl ammonium bromide and ethyl silicate, mixing uniformly, then adding N,N-dimethyl formamide, centrifuging, drying to obtain a solid product; S3, calcining the solid product in a nitrogen atmosphere to obtain nitrogen-doped hollow mesoporous carbon; S4, adding a mixed solution of copper acetylacetonate and an organic solvent, and the nitrogen-doped hollow mesoporous carbon into a solution of acetone to obtain a first mixed solution; S5, ultrasonicating and then heating the first mixed solution to obtain a second product; S6, heating the second product to a preset temperature in a nitrogen atmosphere, and constant temperature calcining to obtain a mesoporous carbon composite material, i.e., nitrogen-doped hollow mesoporous carbon loaded with metal monatomic atoms.

2. The method for preparing a mesoporous carbon composite according to claim 1, characterized by, The base is selected from ammonia water; And / or, the organic solvent is selected from anhydrous ethanol; And / or, in the alkaline water, the volume ratio of the base to water is 0.1-0.3:20-30; And / or, the 3-amino phenol, the formaldehyde, the hexadecyl trimethyl ammonium bromide, the ethyl silicate and the N,N-dimethyl formamide are 0.1-0.3 g:0.1-0.15 mL:0.1-0.3 g:5-10 mL:30-50 mL in terms of g:mL:g:mL:mL; And / or, in the mixed solution of the organic solvent and the base, the volume ratio of the organic solvent to the base is 20-30:0.5-1.5; And / or, the mass ratio of the copper acetylacetonate to the nitrogen-doped hollow mesoporous carbon is 0.15-0.6:0.1-0.

4.

3. The method for preparing mesoporous carbon composite material according to claim 1, characterized in that, In S3, the calcining temperature in the nitrogen atmosphere is 550-800 ℃, and the time is 2-5 h; And / or, in S6, the preset temperature is 600-800 ℃, the constant temperature calcining time is 3-6 h, the heating mode in the nitrogen atmosphere is programmed heating, and the programmed heating rate is 5 ℃ / min; And / or, in S5, the ultrasonicating time is 4 h, the heating reaction temperature is 60-80 ℃, and the time is 6-8 h.

4. Application of the mesoporous carbon composite material prepared by the preparation method in any one of claims 1-3 as a catalyst for catalyzing the degradation of antibiotics in wastewater by persulfate.

5. Use according to claim 4, characterized in that, The persulfate is selected from sodium persulfate; And / or, the antibiotics comprise at least one of tetracycline, oxytetracycline hydrochloride and sulfamethoxazole; And / or, the mass ratio of the persulfate to the mesoporous carbon composite material is 1:0.5-1.5; And / or, when the mass ratio of antibiotics, persulfate and mesoporous carbon composite in sewage is 0.04-0.2:1:0.5-1.5, the time for reducing the antibiotics in the sewage to 0 is 12-20 min.

6. Use according to claim 4, characterized in that, The mesoporous carbon composite is used as a catalyst in a method for catalyzing the degradation of antibiotics in sewage by persulfate, comprising the following steps: The persulfate and the mesoporous carbon composite are added to the sewage containing the antibiotics, mixed uniformly, and then reacted under the conditions of normal temperature and pressure and in the dark to remove the antibiotics in the sewage.

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