Cu-bnc catalyst with double active sites and preparation method and application thereof

Abstract

The application discloses a Cu-BNC catalyst with double active sites and a preparation method and application thereof. The catalyst is prepared from a carbon-nitrogen precursor, a boron source and a copper salt as raw materials through calcination, wherein the double active sites include B-O-Cu active sites and graphite nitrogen active sites. The preparation method is simple in process and convenient in operation, the content of graphite nitrogen is improved through copper doping, the activity of the catalyst is regulated by utilizing the synergistic effect between the double active sites, and the activation performance on persulfate is improved. The Cu-BNC catalyst with double active sites has high catalytic activity and good stability, can be used for activating persulfate and efficiently degrading organic pollutants in water, so that the rapid removal of organic matters in water is realized, the reaction rate is fast, the treatment effect is good, and the rapid degradation of antibiotics in complex actual water can be realized, so that the Cu-BNC catalyst has a good application prospect in industrial wastewater and actual application.

Description

Technical Field

[0001] This invention belongs to the field of wastewater treatment technology, and relates to a Cu-BNC catalyst with dual active sites, its preparation method, and its application. Background Technology

[0002] Due to SO4 ·- Carbon materials have high redox potentials (2.5V-3.1V) and can serve as oxidants for most organic compounds. In recent years, advanced oxidation technologies based on persulfates have become a research hotspot for degrading recalcitrant organic pollutants. Carbon materials have advantages such as ease of synthesis, large specific surface area, and high electrical conductivity, exhibiting excellent efficiency in activating persulfates to degrade organic matter. However, pure carbon materials are costly and have limited catalytic ability due to their chemical inertness and poor stability. Therefore, efforts to regulate the structure and composition of carbon materials, enhance the catalytic region, and improve catalytic ability are inevitable trends.

[0003] Introducing heteroatoms such as nitrogen, boron, sulfur, and phosphorus into the carbon framework alters the chemical properties of carbon materials. Compared to single-element doping, co-doping with two or more elements more readily induces changes in structure and properties, including inducing structural defects, adjusting the charge density of the carbon matrix, enhancing electron mobility, and increasing adsorption energy, which is beneficial for improving catalytic activity. Among various doping elements, boron and nitrogen are considered ideal atoms for co-doping carbon-based materials. This is because the atomic radii of boron and nitrogen are similar to those of carbon, which can maintain a constant total number of electrons in carbon-based materials. Furthermore, the electronegativity of boron and nitrogen differs from that of carbon, allowing them to disrupt the stable sp atoms in carbon materials during high-temperature preparation. 2The electron cloud density and spin structure of hybrid carbon disrupt the chemical inertness of the carbon matrix, forming BC / BO and NC bonds, thereby altering the charge density distribution of the carbon matrix and creating charged catalytically active sites. Various nitrogen structures formed by replacing carbon with nitrogen (such as graphitic nitrogen, pyridine nitrogen, and pyrrole nitrogen) have different effects on the local electronic structure of the carbon matrix, resulting in different catalytic activities. In particular, during the inventors' actual research, it was found that graphitic nitrogen has a stronger charge transfer capacity than pyridine nitrogen and pyrrole nitrogen. Therefore, when the graphitic nitrogen content in carbon materials is relatively high, the carbon materials exhibit superior catalytic activity. However, a common problem in existing heteroatom-doped carbon materials, or those co-doped with boron, nitrogen, and certain metal elements such as iron, is the relatively low graphitic nitrogen content. This results in poor catalytic activity in existing conventional co-doped carbon materials, making it difficult for them to achieve efficient degradation of pollutants in water. To date, no effective method has been found to increase the graphitic nitrogen content in boron-nitrogen-doped carbon materials. Therefore, obtaining a Cu-BNC catalyst with a high graphitic nitrogen content and high catalytic activity and dual active sites is of great significance for achieving efficient removal of pollutants from water bodies. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to overcome the shortcomings of the prior art and provide a Cu-BNC catalyst with dual active sites that can significantly increase the nitrogen content of graphite and has high catalytic activity, as well as its preparation method and application.

[0005] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0006] A method for preparing a Cu-BNC catalyst with dual active sites, wherein the preparation method uses carbon and nitrogen precursors, boron source and copper salt as raw materials and calcines them to obtain a Cu-BNC catalyst with dual active sites.

[0007] In a further improvement to the above-mentioned method for preparing the Cu-BNC catalyst with dual active sites, the mass ratio of the carbon-nitrogen precursor, boron source, and copper salt is 2.5:1:0.03 to 0.1.

[0008] In a further improvement to the above-mentioned method for preparing the Cu-BNC catalyst with dual active sites, the carbon and nitrogen precursor is melamine; the boron source is boric acid; and the copper salt is copper nitrate trihydrate.

[0009] The preparation method of the above-mentioned Cu-BNC catalyst with dual active sites is further improved by including the following steps: dissolving and mixing the carbon-nitrogen precursor, boron source and copper salt, drying, grinding and calcining to obtain the Cu-BNC catalyst with dual active sites.

[0010] In a further improvement to the above-mentioned method for preparing Cu-BNC catalyst with dual active sites, the calcination temperature is 700℃~900℃ and the calcination time is 1h~3h.

[0011] In a further improvement to the above-mentioned method for preparing the Cu-BNC catalyst with dual active sites, the calcination is carried out under a nitrogen atmosphere; the heating rate of the calcination is 3℃ / min to 5℃ / min.

[0012] In a further improvement to the above-mentioned method for preparing Cu-BNC catalyst with dual active sites, the dissolution and mixing are carried out by magnetic stirring, the stirring speed is 300 r / min to 500 r / min, and the stirring temperature is 70℃ to 90℃.

[0013] As a general technical concept, the present invention also provides a Cu-BNC catalyst with dual active sites, which is prepared by the above-described preparation method, wherein the dual active sites include BO-Cu active sites and graphite nitrogen active sites.

[0014] As a general technical concept, the present invention also provides the application of the Cu-BNC catalyst with dual active sites as described above in activated persulfate degradation of organic pollutant wastewater.

[0015] The above-mentioned application, further improved, includes the following steps: mixing the Cu-BNC catalyst with dual active sites with organic pollutant wastewater for pre-adsorption; when the pre-adsorption reaches saturation, adding persulfate to trigger an oxidation reaction to complete the degradation of the organic pollutant wastewater; the amount of Cu-BNC catalyst with dual active sites added is 0.1g to 0.2g per liter of organic pollutant wastewater; the amount of persulfate added is 0.5mmol to 1mmol per liter of organic pollutant wastewater; the initial concentration of organic pollutants in the organic pollutant wastewater is 10mg / L to 20mg / L.

[0016] In the above-described application, a further improvement is made where the persulfate is permonosulfate; the organic pollutant wastewater is tetracycline antibiotic wastewater; the pre-adsorption time is 20 min to 40 min; and the oxidation reaction time is 20 min to 60 min.

[0017] In the above-described application, and further improved, the tetracycline antibiotic is tetracycline.

[0018] Compared with the prior art, the advantages of the present invention are as follows:

[0019] (1) The preparation method of the present invention uses carbon-nitrogen precursors, boron sources, and copper salts as raw materials to calcine and prepare Cu-BNC catalysts with dual active sites. Cu-BNC catalysts with BO-Cu active sites and graphitic nitrogen active sites are prepared by co-doping copper with non-metallic compounds (B, N, O). Copper doping increases the graphitic nitrogen content, thereby improving the catalyst activity. The dual active sites obtained by co-doping copper, boron, and nitrogen synergistically further enhance the catalyst activity. Specifically, in the present invention, copper doping promotes the conversion of pyridine nitrogen to graphitic nitrogen, thereby significantly increasing the graphitic nitrogen content in the catalyst. Graphitic nitrogen is a non-radical active site, which gives the catalyst of the present invention a stronger charge transfer capability, promoting the adsorption and electron transfer of persulfate, thus improving the catalyst's activation performance. However, sufficient graphitic nitrogen cannot be obtained by doping carbon materials with elements such as boron, nitrogen, and iron alone. Therefore, the present invention, through copper doping, promotes the conversion of pyridine nitrogen to graphitic nitrogen, overcoming the technical difficulty of increasing the proportion of graphitic nitrogen in the catalyst, thereby significantly improving the catalyst's activation performance. More importantly, a synergistic effect exists between the dual-active-site BO-Cu active sites and the graphitic nitrogen active sites. Electron transfer in the electron-rich region formed around the copper sites in the BO-Cu active sites promotes the activation of persulfate. Monovalent copper reacts with the adsorbed persulfate to generate active free radicals, which are then converted into divalent copper. Subsequently, divalent copper chemically bonds with persulfate to form complex intermediates. These intermediates gain electrons from electron-rich organic matter and decompose into non-free radicals. Boron promotes the cycling of monovalent and divalent copper, thereby promoting the overall synergistic effect of the dual-active-site system. In summary, copper doping of the present invention can further increase the active sites of carbon materials and improve catalytic efficiency. The synergistic effect of the dual-active-site system can expose more active sites, thereby obtaining high-efficiency activity. Currently, there are no reports on the influence of the connection and interaction between active sites in copper and boron / nitrogen co-doped carbon catalysts on the catalytic process. The preparation method of the present invention provides a reference for the rational design, simple preparation process, and superior performance of metal-nonmetal co-coordinated carbon-based catalysts.

[0020] (2) The preparation method of the present invention further promotes the conversion of pyridine nitrogen to graphitic nitrogen by optimizing the raw material ratio, especially the amount of copper doping, thereby maximizing the content of graphitic nitrogen active sites and further enhancing the synergistic effect of the two active sites, thus enabling the catalyst to exhibit superior catalytic activity.

[0021] (3) The preparation method of the present invention uses low-priced raw materials, simple preparation process, convenient operation, and low requirements for preparation conditions and equipment, which makes the catalyst preparation cost low, can form a chain production, and is easy to produce on a large scale.

[0022] (4) The Cu-BNC catalyst with dual active sites of the present invention has high catalytic activity, good activation effect on persulfate, high degradation efficiency for activating persulfate to degrade antibiotic wastewater, and can also tolerate the interference of natural organic matter in actual water bodies. It has shown high efficiency in the removal of antibiotics in actual natural water bodies and has good practical application potential. Attached Figure Description

[0023] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings.

[0024] Figure 1 This is a scanning electron microscope image of the Cu-BNC catalyst with dual active sites prepared in Example 1 of the present invention.

[0025] Figure 2 The images show the ATR-FTIR spectra of the Cu-BNC catalysts with dual active sites prepared in Examples 1-3 of this invention.

[0026] Figure 3 This is an XPS image of the Cu-BNC catalyst with dual active sites prepared in Example 1 of this invention.

[0027] Figure 4 High-resolution N1s images of the catalysts prepared in Example 1 and Comparative Example 1 of this invention.

[0028] Figure 5 The images show the electrochemical impedance spectroscopy diagrams of the catalysts prepared in Examples 1-3 and Comparative Example 1 of this invention.

[0029] Figure 6 This is a diagram showing the degradation effect of different catalysts on tetracycline in water in Example 4 of the present invention.

[0030] Figure 7 This is a diagram showing the degradation effect of Cu-BNC catalyst with dual active sites on tetracycline in different water bodies in Example 5 of the present invention. Detailed Implementation

[0031] The present invention will be further described below with reference to the accompanying drawings and specific preferred embodiments, but this does not limit the scope of protection of the present invention.

[0032] In the following examples, unless otherwise specified, the raw materials and instruments used are commercially available, the equipment used is conventional equipment, and the data obtained are the average values ​​of more than three repeated experiments.

[0033] Example 1

[0034] A method for preparing a Cu-BNC catalyst with dual active sites includes the following steps:

[0035] Melamine, boric acid, and copper nitrate trihydrate in a mass ratio of 2.5:1:0.05 were dissolved in deionized water and mixed by magnetic stirring at 400 r / min and 80 °C. The mixture was then dried to obtain a final product. The final product was ground in an agate mortar and transferred to a tube furnace. Under a nitrogen atmosphere, the temperature was increased to 800 °C at a rate of 3 °C / min and maintained for 2 h for calcination to obtain a Cu-BNC catalyst with dual active sites. The mass ratio of Cu to BNC in the obtained product was 1.5%, denoted as 1.5% Cu-BNC.

[0036] Example 2

[0037] The preparation method of a Cu-BNC catalyst with dual active sites is basically the same as that of Example 1, except that the amount of copper doping is different, specifically the ratio of raw materials. In this example, the mass ratio of melamine, boric acid and copper nitrate trihydrate is 2.5:1:0.03, and the mass ratio of Cu to BNC in the obtained product is 1%, denoted as 1% Cu-BNC.

[0038] Example 3

[0039] The preparation method of a Cu-BNC catalyst with dual active sites is basically the same as that of Example 1, except that the amount of copper doping is different, specifically the ratio of raw materials. In this example, the mass ratio of melamine, boric acid and copper nitrate trihydrate is 2.5:1:0.1, and the mass ratio of Cu to BNC in the obtained product is 3%, denoted as 3% Cu-BNC.

[0040] Comparative Example 1

[0041] A method for preparing a BNC catalyst includes the following steps:

[0042] Melamine and boric acid in a mass ratio of 2.5:1 were dissolved in deionized water and mixed by magnetic stirring at 400 r / min and 80 °C. The mixture was then dried to obtain a powder. The powder was ground in an agate mortar and then transferred to a tube furnace. Under a nitrogen atmosphere, the powder was heated to 800 °C at a rate of 3 °C / min and held for 2 h to obtain the BNC catalyst.

[0043] The Cu-BNC catalyst (1.5% Cu-BNC) with dual active sites prepared in Example 1 of this invention was analyzed by scanning electron microscopy, and the results are as follows: Figure 1 As shown.

[0044] The Cu-BNC catalysts with dual active sites prepared in Examples 1-3 of this invention were subjected to ATR-FTIR analysis, and the results are as follows: Figure 2 As shown in the figure, 3400cm -1 The nearby peak is attributed to the stretching vibration of the OH group. Approximately 1670 cm⁻¹ -1 The Fourier transform infrared band at that location can be attributed to sp 2 Oscillations in the C=C valence state on the surface of hybrid graphite carbon. 1380 cm⁻¹ -1 and 1030cm -1 The characteristic peaks at this location are attributed to CN and BO. Furthermore, Cu-O corresponds to a peak at 488 cm⁻¹. -1 The peak value directly confirms the successful preparation of the Cu-BNC catalyst and the successful synthesis of the BO-Cu site.

[0045] XPS analysis was performed on the Cu-BNC catalyst (1.5% Cu-BNC) with dual active sites prepared in Example 1 of this invention. The results are as follows: Figure 3 As shown, X-ray photoelectron spectroscopy revealed that 1.5% Cu-BNC is composed of Cu, B, C, N, and O elements, further confirming the successful preparation of the Cu-BNC catalyst.

[0046] The Cu-BNC catalyst (1.5% Cu-BNC) with dual active sites prepared in Example 1 of this invention was subjected to high-resolution N1s spectral analysis, and the results are as follows: Figure 4 As shown in the figure, the peaks of BNC at 397.6 eV, 398.74 eV, and 400.03 eV are attributed to pyridine nitrogen, pyrrole nitrogen, and graphitic nitrogen, respectively. In contrast, the peak area of ​​graphitic nitrogen in 1.5% Cu-BNC is significantly increased. This phenomenon suggests that the successful synthesis of the graphitic nitrogen active site in 1.5% Cu-BNC may be due to copper enhancing the conversion of pyridine nitrogen to graphitic nitrogen. Graphitic nitrogen is a non-radical active site that can promote the catalytic reaction. This conclusion is confirmed in Example 4.

[0047] Electrochemical impedance spectroscopy was performed on the Cu-BNC catalysts with dual active sites prepared in Examples 1-3 of this invention. The results are as follows: Figure 5As shown, the electron transfer performance of the Cu-BNC catalyst was verified by electrochemical impedance spectroscopy. The smaller diameter of the semicircle in the electrochemical impedance spectroscopy indicates a lower charge transfer resistivity of the material. In the figure, 1.5% Cu-BNC has the lowest charge transfer resistance, while BNC has the highest. The lowest charge transfer resistance of 1.5% Cu-BNC indicates that its electron transfer performance is the best, which is consistent with the optimal degradation results of 1.5% Cu-BNC for organic pollutants in oxidative degradation applications. That is, the electrochemical performance of 1.5% Cu-BNC prepared after optimizing the copper doping ratio is improved. This improvement is conducive to the electron transfer process, thereby improving the degradation effect.

[0048] Example 4

[0049] An application of a Cu-BNC catalyst with dual active sites, specifically involving the activation of persulfate with a Cu-BNC catalyst with dual active sites to efficiently degrade tetracycline in water, includes the following steps:

[0050] Take 10 mg each of the Cu-BNC catalysts with dual active sites (1% Cu-BNC, 1.5% Cu-BNC, and 3% Cu-BNC) prepared in Examples 1-3 and the BNC catalyst prepared in Comparative Example 1, and place them in 50 ml of a tetracycline solution with a concentration of 20 mg / L. Stir for 30 minutes for pre-adsorption. After the pre-adsorption reaches saturation, add 0.5 mmol (0.0077 g) of persulfate (PMS) to carry out the catalytic degradation reaction and complete the degradation of tetracycline in the water.

[0051] During the catalytic reaction, 1 ml of tetracycline solution was taken at regular intervals, filtered through a 0.22 μm membrane filter, and the reaction was terminated with 20 μL of 0.1 mol / L sodium thiosulfate solution. The concentration of the remaining tetracycline was measured using high-performance liquid chromatography (HPLC), and the degradation efficiency of different catalysts for tetracycline under different time conditions was calculated. The results are as follows: Figure 5 As shown.

[0052] Figure 6 This is a graph showing the degradation effect of different catalysts on tetracycline in water in Example 4 of the present invention. Figure 6It can be seen that, compared with the BNC catalyst of Comparative Example 1, the Cu-BNC catalyst with dual active sites prepared in this invention can effectively activate persulfate, thereby efficiently degrading tetracycline in water. In particular, when the mass ratio of melamine:boric acid:copper nitrate trihydrate is 2.5:1:0.05, the prepared Cu-BNC with dual active sites as a catalyst (1.5% Cu-BNC) can degrade 97.63% of tetracycline within 30 minutes. This also shows that the amount of copper doping has an important influence on the activity of the catalyst. Too high or too low a doping amount will have adverse effects. Examples 1-3 further enhanced the promoting effect of copper on the conversion of pyridine nitrogen to graphitic nitrogen by optimizing the amount of copper doping, and at the same time further improved the synergistic effect between the BO-Cu active sites and the graphitic nitrogen active sites, maximizing the activity of the catalyst and thus greatly improving the reaction efficiency of the catalytic reaction. The Cu-BNC catalyst of this invention, which has dual active sites, is a high-performance heterogeneous Fenton-like catalyst with excellent ability to activate persulfate and can efficiently remove organic pollutants from water.

[0053] Example 5

[0054] An application of a Cu-BNC catalyst with dual active sites for activating persulfate degradation of tetracycline in real water bodies is disclosed. Specifically, the application involves treating real water bodies containing tetracycline using a Cu-BNC catalyst (1.5% Cu-BNC) with dual active sites, including the following steps:

[0055] Four groups of Cu-BNC catalysts (1.5% Cu-BNC) with dual active sites prepared in Example 1, 10 mg each, were placed in 50 ml of actual water samples containing 20 mg / L tetracycline. The mixtures were stirred for 30 minutes for pre-adsorption. After pre-adsorption saturation, 0.5 mmol (0.0077 g) of permonosulfate (PMS) was added to catalytically degrade the tetracycline in the actual water. The actual water samples were from the Xiangjiang River and Taozi Lake, with ultrapure water containing the same concentration of tetracycline used as a control.

[0056] During the catalytic reaction, 1 ml of tetracycline solution was taken at regular intervals, filtered through a 0.22 μm membrane filter, and the reaction was terminated with 20 μL of 0.1 mol / L sodium thiosulfate solution. The concentration of the remaining tetracycline was measured using high-performance liquid chromatography (HPLC), and the degradation efficiency of different catalysts for tetracycline under different time conditions was calculated. The results are as follows: Figure 7 As shown.

[0057] Figure 7 This image shows the degradation effect of the Cu-BNC catalyst with dual active sites in different water bodies in Example 5 of this invention. Figure 7It can be seen that the degradation efficiency of tetracycline in the two actual water bodies is slightly lower than that in the ultrapure water system. This is attributed to the presence of a large amount of free organic matter in the actual water bodies and the fact that some organic matter consumes the active substances produced by the reaction. However, the final removal efficiency of tetracycline can still reach more than 92% within 30 minutes. This indicates that the Cu-BNC catalyst with dual active sites has broad practical application prospects and value in activating persulfate to remove antibiotics from actual water bodies.

[0058] In summary, this invention uses melamine, boric acid, and copper nitrate trihydrate as raw materials, and through magnetic stirring, grinding, and calcination, prepares a Cu-BNC catalyst with dual active sites, including BO-Cu active sites and graphitic nitrogen active sites. The preparation method provided by this invention is simple and convenient to operate. Furthermore, by utilizing the synergistic effect between the BO-Cu and graphitic nitrogen active sites, the catalyst activity is controlled, resulting in a catalyst with high activity and good stability. When applied to the activation of persulfate for organic matter degradation, it exhibits a fast reaction rate and good treatment effect. Moreover, it can achieve rapid degradation of antibiotics in complex real-world water bodies. This simple synthesis method and unique structure provide new ideas for the preparation of metal- and non-metal co-doped carbon-based catalysts and their application in wastewater treatment, showing great promise for industrial wastewater treatment and practical applications.

[0059] While the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the invention. Any person skilled in the art can make many possible variations and modifications to the technical solutions of the present invention, or modify them into equivalent embodiments, without departing from the scope of the present invention. Therefore, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention, without departing from the scope of the present invention, should fall within the protection scope of the present invention.

Claims

1. The application of a Cu-BNC catalyst with dual active sites in activated persulfate degradation of organic pollutant wastewater, characterized in that, The Cu-BNC catalyst with dual active sites is prepared by calcination of carbon-nitrogen precursor, boron source and copper salt as raw materials; the organic pollutant wastewater is antibiotic wastewater; the mass ratio of carbon-nitrogen precursor, boron source and copper salt is 2.5∶1∶0.03~0.1; the preparation method includes the following steps: dissolving and mixing the carbon-nitrogen precursor, boron source and copper salt, drying, grinding and calcining to obtain the Cu-BNC catalyst with dual active sites.

2. The application of the Cu-BNC catalyst with dual active sites according to claim 1 in activated persulfate degradation of organic pollutant wastewater, characterized in that, The carbon-nitrogen precursor is melamine; the boron source is boric acid; and the copper salt is copper nitrate trihydrate.

3. The application of the Cu-BNC catalyst with dual active sites according to claim 1 in activated persulfate degradation of organic pollutant wastewater, characterized in that, The calcination is carried out under a nitrogen atmosphere; the heating rate of the calcination is 3℃ / min to 5℃ / min; the calcination temperature is 700℃ to 900℃; and the calcination time is 1h to 3h.

4. The application of the Cu-BNC catalyst with dual active sites according to claim 1 in activated persulfate degradation of organic pollutant wastewater, characterized in that, The dissolution and mixing are carried out by magnetic stirring, the magnetic stirring speed is 300 r / min to 500 r / min, and the magnetic stirring temperature is 70℃ to 90℃.

5. The application of the Cu-BNC catalyst with dual active sites according to any one of claims 1 to 4 in activated persulfate degradation of organic pollutant wastewater, characterized in that, The dual active sites include BO-Cu active sites and graphitic nitrogen active sites.

6. The application of the Cu-BNC catalyst with dual active sites according to claim 5 in activated persulfate degradation of organic pollutant wastewater, characterized in that, The method includes the following steps: mixing a Cu-BNC catalyst with dual active sites with organic pollutant wastewater for pre-adsorption; when the pre-adsorption reaches saturation, adding persulfate to trigger an oxidation reaction to complete the degradation of the organic pollutant wastewater; the amount of Cu-BNC catalyst with dual active sites added is 0.1g to 0.2g per liter of organic pollutant wastewater; the amount of persulfate added is 0.5mmol to 1mmol per liter of organic pollutant wastewater; and the initial concentration of organic pollutants in the organic pollutant wastewater is 10mg / L to 20mg / L.

7. The application of the Cu-BNC catalyst with dual active sites according to claim 6 in activated persulfate degradation of organic pollutant wastewater, characterized in that, The persulfate is permonosulfate; the antibiotic wastewater is tetracycline antibiotic wastewater; the pre-adsorption time is 20 min to 40 min; the oxidation reaction time is 20 min to 60 min.

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