Application of porous carbon material catalyst prepared by microwave carbonization of waste plastics in degradation of organic pollutants

Abstract

The application adopts microwave pyrolysis of waste plastic polyethylene terephthalate (PET) to prepare porous carbon catalytic material, and applies it to peroxymonosulfate (PMS) catalytic activation to degrade organic pollutants such as carbamazepine (CBZ). Microwave absorber cobalt nitrate and initial carbonized alpha-cellulose are used to assist the carbonization of waste plastic PET, and thiourea is used as a metal sulfidation reagent to prepare the waste plastic derived porous carbon material catalyst in a commercial microwave oven with a power of 800W for 10 minutes. The formation of cobalt oxide, the generation of cobalt sulfide, the introduction of C=O and oxygen vacancies, and the increase of specific surface area are all conducive to the improvement of the degradation performance of the catalyst to organic pollutants. The best catalyst S 0.3 -Co@P2C can achieve 100% CBZ degradation in 15 min, and the rate constant is 0.7445 min ‑1 . Compared with the traditional pyrolysis method, the microwave treated carbon material is not only more conducive to the formation and exposure of active sites (CoS and CoO) in the catalytic material, but also conducive to the generation of SO4 •‑ ·OH, O2 •‑ and 1 O2 by PMS catalytic activation. In addition, the introduction of PET is conducive to the formation of C=O in the catalytic material to promote PMS activation and accelerate the non-radical pathway to degrade CBZ.

Description

TECHNICAL FIELD

[0001] The application relates to application of a porous carbon material catalyst prepared by microwave carbonization of waste plastics in degradation of organic pollutants. BACKGROUND

[0002] The management of plastic waste has become a global problem in today's era. Domestic and foreign research results show that microplastics generated by waste polymer materials have caused pollution to organisms in oceans and rivers and drinking water, and it is imperative to solve the problem of "white pollution". Due to the unique properties of carbon materials, such as high surface area, porosity and electronic conductivity, rich / controllable surface chemical properties and structural stability at high temperatures, it has become one of the research hotspots at the present stage to make waste plastics into carbon materials. So far, the few microwave-assisted degradation methods of waste plastics are still very complex. How to convert waste plastics into carbon material catalysts under the action of microwaves and apply them to the efficient catalysis of processes is still unreported and has strong challenge.

[0003] Pharmaceuticals and personal care products found in the environment and wastewater have been identified as emerging pollutants. Due to the increase in consumption and incomplete removal, antibiotics have been found in natural waters all over the world. Carbamazepine (CBZ) is an antibiotic commonly used to treat epilepsy and depression, which can enter the aquatic environment through different routes and persist, CBZ is structurally stable and non-biodegradable. In addition, the long-term presence of CBZ in the water environment will directly or indirectly affect the quality of drinking water and thus endanger human health. However, some traditional methods (such as adsorption, filtration, biological methods or electrochemical oxidation) are difficult to effectively degrade CBZ. Therefore, it is urgent to develop efficient and environmentally friendly CBZ degradation methods. The general method of PMS activation mainly includes heating, ultraviolet irradiation, microwave and transition metal ions. Transition metal oxides (M x O y ), involving Co, Fe, Cu and Mn oxides, are considered to be effective low-dose PMS activators. Previous studies have shown that the enrichment of metal sulfides, oxygen vacancies, the increase of specific surface area and the construction of porous structure in the catalytic material can significantly promote the activation of PMS.

[0004] For the preparation of carbon materials, microwave technology has been proven to be more effective than traditional pyrolysis in energy transfer, improving carbon material yield and immediate and accurate time control. Iron, cobalt, aluminum and other metal oxides are widely used as microwave absorbers due to their low cost, high dielectric loss coefficient and ability to absorb high doses of microwaves. So far, there has been no report on the method of using microwaves to treat waste plastics for carbonization. SUMMARY

[0005] The application uses waste plastic polyethylene terephthalate (PET) as raw material, cobalt nitrate as microwave absorber and catalytic activation center, alpha-cellulose as carbonization auxiliary agent, and thiourea as metal sulfuration reagent, mixes all the solid materials uniformly by using a mortar, and then prepares the waste plastic derived carbon material catalyst with porous morphology by using simple microwave assisted pyrolysis for 10 minutes.

[0006] The application discloses application of a porous carbon material catalyst prepared by microwave carbonization of waste plastics in degradation of organic pollutants, and is characterized in that: a simple microwave pyrolysis method is used, waste plastic polyethylene terephthalate (PET) is used as raw material, cobalt nitrate is used as microwave absorber and catalytic activation center, alpha-cellulose is used as carbonization auxiliary agent, and thiourea is used as metal sulfuration reagent, and the waste plastic derived carbon material catalyst with porous morphology is rapidly synthesized by pyrolysis in a microwave oven with a power of 800 W for 10 minutes.

[0007] The preparation steps of the porous carbon material catalyst are as follows: 0.230 g of PET powder, 0.230 g of Co (NO3) 2·6H2O (0.8 mmol), 0.115 g of alpha-cellulose powder and 0.025 g of thiourea (0.3 mmol) are weighed, uniformly ground and mixed in a ceramic mortar, then the mixture is placed in a 25 mL crucible, pyrolysis is carried out in a commercial microwave oven with a power of 800 W for 10 minutes, after the material is cooled, water / ethanol washing and vacuum drying are carried out, and the porous carbon catalyst material S 0.3 -Co@P2C; when the dosage of thiourea is 0.1, 0.2, 0.3, 0.4 and 0.5 mmol, the prepared catalyst is named S x -Co@P2C (x = 0.1, 0.2, 0.3, 0.4 and 0.5); when the dosage of thiourea is 0.3 mmol, the total mass of the PET powder and the alpha-cellulose powder is kept as 0.345 g, and the mass ratio of the PET powder to the cellulose powder is changed according to the ratio of 1:1, 2:1 and 4:1, and at this time, the prepared catalyst is named S 0.3 -Co@P y C (y = 1, 2 and 4);

[0008] Catalyst activation peroxymonosulfate (PMS) degradation of organic pollutants: using a constant temperature magnetic stirring water bath to control the temperature, using 1M sulfuric acid or sodium hydroxide to adjust the initial pH, adding a set concentration of catalyst and PMS to start the degradation process in a 100 mL round bottom flask containing 50 mL of organic pollutant (20 mg / L) aqueous solution; extract 1 mL of reaction solution at predetermined time intervals, filter using a 0.25 µm microporous membrane, squeeze into a centrifuge tube containing 2 mL of methanol, and determine the concentration of organic pollutants using a UV-visible spectrophotometer.

[0009] The application of the above-mentioned porous carbon material catalyst prepared by microwave carbonization of waste plastics in the degradation of organic pollutants is characterized by: the preparation process of the catalyst is simple, the preparation time is short, and the optimal catalyst exhibits obvious porous morphology structure characteristics; compared with traditional pyrolysis methods, microwave treatment and the introduction of PET are beneficial to the formation of metal oxides, metal sulfides, C=O and oxygen vacancies and the expansion of the specific surface area of the catalyst material.

[0010] The application of the above-mentioned porous carbon material catalyst prepared by microwave carbonization of waste plastics in the degradation of organic pollutants is characterized by: the prepared porous carbon material catalyst S 0.3 -Co@P2C has high degradation efficiency for organic pollutants, and the removal rate of carbamazepine can reach 100.0 % within 15 min, and the rate constant reaches 0.7445 min −1 ; the removal rates of methyl orange, tetracycline hydrochloride, oxytetracycline hydrochloride, ciprofloxacin and rhodamine B pollutants can all reach 100%, 100%, 100%, 93.9% and 98.6%, which confirms that S 0.3 -Co@P2C / PMS catalytic system has good degradation ability for different organic pollutants.

[0011] The application of the above-mentioned porous carbon material catalyst prepared by microwave carbonization of waste plastics in the degradation of organic pollutants is characterized by: in S 0.3 -Co@P2C / PMS catalytic system, PMS is catalytically activated to generate SO4 •- , ·OH, O2 •- and 1 O2, among which SO4 •- and O2 •- are the main active substances for pollutant degradation, 1 O2 and ·OH are secondary active substances.

[0012] Drawings of the specification

[0013] Figure 1 (a, b) are SEM images of S 0.3 -Co@P2C, Figure 1(c, d) are S 0.3 TEM images of Co@P2C, Figure 1 (e) is S 0.3 HRTEM images of Co@P2C.

[0014] Figure 2 (a) is catalyst S 0.3 -Co@P0C, S 0.3 -Co@P1C, S 0.3 -Co@P2C, S 0.3 -Co@P4C, S 0.3 -Co@P2C 700 X-ray diffraction (XRD) patterns of CoO; Figure 2 (b) is S 0.1 -Co@P2C, S 0.2 -Co@P2C, S 0.3 -Co@P2C, S 0.4 -Co@P2C, S 0.5 -Co@P2C, S 0.3 -Co@P2C 700 XRD patterns of CoO; Figure 2 (c) is S 0.3 -Co@P2C and S 0.3 -Co@P2C 700 Raman spectra comparison; Figure 2 (d) is S 0.3 -Co@P2C and CoO Raman spectra comparison; Figure 2 (e) is S 0.3 -Co@P2C, S 0.3 -Co@P2C 700 and S 0.3 N2adsorption / desorption isotherms of Co@P0C (inset: pore size distribution).

[0015] Figure 3 is catalyst S 0.3 -Co@P2C, S 0.3 -Co@P2C 700 and S 0.3 X-ray photoelectron spectroscopy (XPS) of Co@P0C. (a) full spectrum, (b) Co 2p, (c) S 2p, (d) C 1s, (e) O 1s. DETAILED DESCRIPTION

[0016] The application will be described in detail below with specific implementation cases.

[0017] Implementation Case 1:

[0018] The specific preparation steps of porous carbon catalysts are as follows:

[0019] Weigh 0.230 g PET powder, 0.230 g Co(NO3)2·6H2O (0.8 mmol), 0.115 g α-cellulose powder, and 0.025 g thiourea (0.3 mmol). Mix them evenly in a ceramic mortar. Place the mixture in a 25 mL crucible and pyrolyze it in an 800 W commercial microwave oven for 10 min. After cooling, wash with water / ethanol and vacuum dry to obtain porous carbon catalyst S. 0.3 -Co@P2C; When the dosage of thiourea was 0.1, 0.2, 0.3, 0.4, and 0.5 mmol, the prepared catalyst was named S. x -Co@P2C (x = 0.1, 0.2, 0.3, 0.4, and 0.5); when the amount of thiourea is 0.3 mmol, the total mass of PET powder and α-cellulose powder is kept at 0.345 g, and the mass ratio of PET powder to α-cellulose powder is changed at ratios of 1:1, 2:1, and 4:1. The catalyst prepared under these conditions is named S. 0.3 -Co@P y C (y = 1, 2, and 4); Furthermore, a catalyst S was prepared without the addition of PET powder. 0.3 -Co@P0C; with S 0.3 The difference in the preparation process of -Co@P2C is that S 0.3 -Co@P2C 700 The catalyst was obtained by pyrolysis at 700°C for 3 hours in a flowing N2 atmosphere using a tube furnace. For comparison, while maintaining a constant mass ratio of PET powder to α-cellulose powder of 2:1, S@P2C catalyst without cobalt nitrate, Co@P2C catalyst without thiourea, and Co@P0C catalyst containing only cobalt nitrate and 0.345 g of α-cellulose powder were also prepared. The prepared catalyst S... 0.3 -Co@P2C、S 0.3 -Co@P2C 700 S 0.3 The specific surface area of ​​-Co@P0C is 32.97 m². 2 / g, 21.63m 2 / g, 16.94 m 2 / g.

[0020] Figure 1 (a,b) is S 0.3 SEM images of -Co@P2C Figure 1 (c,d) is S 0.3 -TEM image of Co@P2C, Figure 1 (e) is S0.3 HRTEM image of Co@P2C. The morphology structure of the catalysts was characterized by scanning electron microscopy (SEM), and it was found that S 0.3 -Co@P2C catalytic materials exhibited obvious porous structure characteristics. From Figure 1 It can also be seen in (c, d) that S 0.3 -Co@P2C catalytic materials presented a porous structure, and cobalt nanoparticles were uniformly dispersed on the carbon material with an average particle size of 29.9 nm. The lattice fringes with spacings of 0.217 nm and 0.196 nm observed in the HRTEM image of Fig. 1 (e) correspond to the (200) plane of CoO and the (102) plane of CoS, respectively. S 0.3 The coexistence of CoO and CoS in the Co@P2C catalytic material would be very beneficial to the degradation of pollutants.

[0021] Figure 2 (a, b) is the characterization of the crystal structure of the prepared catalytic material by X-ray diffraction (XRD). No diffraction peak of PET was observed in all catalysts, indicating the successful carbonization of waste plastic PET. Porous carbon catalytic material S 0.3 The XRD pattern of Co@P2C shows a series of peaks at 36.4 o , 42.3 o , 61.5 o , 73.6 o and 77.5 o , corresponding to the (111), (200), (220), (311) and (222) crystal planes of CoO. In addition to the peaks of CoO, peaks at 29.9 o , 31.3 o and 47.5 o were also obviously observed, corresponding to the (100), (002) and (102) crystal planes of CoS. The smaller peaks at 44.3 o and 53.1 o should be resolved as the (111) and (200) crystal planes of metallic Co. Compared with S 0.3 -Co@P2C prepared by microwave carbonization, the catalytic material S 0.3 -Co@P2C 700 prepared by traditional pyrolysis 0.3 The diffraction peaks of CoO, CoS and metallic Co in S Figure 2 -Co@P2C are not as obvious as those in S 0.3 -Co@P2C prepared by microwave treatment, which indicates that the carbon material catalyst prepared by microwave treatment is more conducive to the exposure of active sites. It was further investigated that the initial ratio of PET to a-cellulose affected the formation of active species in the catalytic material, and compared with S0.3 -Co@P0C, the introduction of PET is beneficial to the formation of catalytic active sites (CoO and CoS) (S 0.3 -Co@P1C, S 0.3 -Co@P2C vs S 0.3 -Co@P0C). When the mass ratio of PET to cellulose is further increased to 4:1, the diffraction peaks of CoO and CoS are obviously weakened, and the diffraction peak of metallic Co is observed, which is not conducive to the improvement of the performance of the catalyst in degrading pollutants. In Figure 2 b, the effect of the amount of thiourea on the active species in the catalytic material is investigated. With the increase of the amount of thiourea from 0.1 mmol to 0.2 mmol and 0.3 mmol, the intensity of the CoS diffraction peak is obviously enhanced, but further increasing the amount of thiourea, the intensity of the CoO diffraction peak is significantly reduced, and excessive metal sulfide obviously affects the formation of other catalytically active species. Therefore, S 0.3 -Co@P2C is the best catalyst for carbonization of microwave-treated waste plastic PET. Figure 2 c is to analyze the effect of pyrolysis method on S 0.3 -Co@P2C, S 0.3 -Co@P2C 700 Raman spectrum test is carried out to analyze the influence of fine structure of carbon in the sample. In S 0.3 -Co@P2C and S 0.3 -Co@P2C 700 The G (1581 cm -1 ) band and D (1357 cm -1 ) band are detected in all samples, which represent the hexagonal bonded carbon atoms and the defective carbon structure in the graphite network, respectively. The intensity ratio (I D / I G ) of D band and G band represents the disorder and defect degree of carbon material. S 0.3 -Co@P2C has an I D / I G value of 1.08, which is greater than the I 0.3 / I 700 value of 0.90 of S D -Co@P2C G , which indicates that the microwave-treated carbon catalyst material S 0.3 -Co@P2C is more prone to form defective carbon. Figure 2 d is the Raman spectrum of S 0.3 -Co@P2C and CoO. From the spectrum, it can be seen that the Co-O vibration peak of CoO is located at 208, 498, 537, 638 and 706 cm -1 . The Raman peaks at 208, 498 and 638 cm -1 are the F 2gPattern, and at 537 and 706 cm -1 The peaks at these locations represent the E values ​​of cobalt suboxide. g Pattern and A 1g Pattern. Compared to CoO, S 0.3 -Co@P2C Co-O A 1g The model peak broadened while redshifting to 681 cm⁻¹ -1 This indicates that S 0.3 -Co@P2C contains a large number of oxygen vacancies in its CoO phase. The S content was determined using a BET nitrogen adsorption-desorption isotherm. 0.3 -Co@P2C、S 0.3 -Co@P2C 700 and S 0.3 -Specific surface area of ​​Co@P0C catalytic material ( Figure 2 e). S 0.3 -Co@P2C、S 0.3 -Co@P2C 700 and S 0.3 -Co@P0C exhibits a type IV isotherm with a hysteresis loop, indicating a mesoporous structure. (Compared to S...) 0.3 -Co@P0C (16.94 m) 2 Compared to / g), S 0.3 -Co@P2C (32.97 m) 2 The specific surface area and pore capacity of the PET ( / g) increased significantly, indicating that the introduction of PET is beneficial to the formation of porous carbon materials with a large specific surface area. Meanwhile, S 0.3 -Co@P2C(32.97 m 2 The specific surface area and pore capacity of ( / g) are also greater than those of S. 0.3 -Co@P2C 700 (21.63m) 2 / g), which indicates that microwave pyrolysis is beneficial for increasing the specific surface area and pore capacity during the construction of catalytic materials.

[0022] Figure 3 The surface chemical state of the catalyst was determined using X-ray photoelectron spectroscopy (XPS). In S... 0.3 -Co@P2C、S 0.3 -Co@P2C 700 and S 0.3 Characteristic peaks of C, O, Co, and S elements were clearly detected in the full spectrum of the -Co@P0C composite material (Figure 3a). The detection of S in the catalytic material indicates successful sulfidation of the catalyst by thiourea. The Co 2p spectrum shows Co 2p... 1 / 2 and Co 2p 3 / 2 Two sets of peaks ( Figure 3b). The peaks at 796.98 and 781.48 eV are attributed to Co 2p of Co(II) 1 / 2 and Co 2p 3 / 2 c). The peaks at 794.18 and 779.08 eV are attributed to Co 2p of Co(III) 1 / 2 and Co 2p 3 / 2 In addition, there are satellite peaks at 802.98 and 786.38 eV. The ratio of S 0.3 -Co@P0C and S 0.3 -Co@P2C, the introduction of waste plastic PET is obviously conducive to the formation of metal oxides. Compared with the traditional pyrolysis prepared catalytic material S 0.3 -Co@P2C 700 , the microwave treated S 0.3 -Co@P2C has higher Co 2+ content, indicating that microwave treatment is conducive to the production of Co 2+ . Since the metal sulfuration process also consumes Co 3+ , microwave treatment should be more conducive to the sulfuration of metals. Figure 3 (c) is the S 2p spectrum of S 0.3 -Co@P2C, S 0.3 -Co@P2C 700 and S 0.3 -Co@P0C. The peak at 162.68 eV should be attributed to S 2- , and the peaks at 169.78 and 168.58 eV correspond to surface-bound sulfite and sulfate, respectively. The S 0.3 peak intensity of S 2- -Co@P2C is obviously higher than that of S 0.3 -Co@P2C 700 and S 0.3 -Co@P0C, indicating that both microwave treatment and the introduction of PET are conducive to the sulfuration of the catalytic material. Figure 3 (d) The XPS spectrum of C 1s can be resolved into three peaks at 288.08, 286.38 and 284.80 eV, corresponding to C=O, C-O and C=C, respectively. From the spectrum, it can be observed that the content of C=O is S 0.3 -Co@P2C > S 0.3 -Co@P2C 700 > S 0.3 -Co@P0C, indicating that both the introduction of PET and microwave treatment are conducive to the formation of C=O. C=O in the catalytic material will be conducive to the activation of PMS to produce 1 O2, thereby accelerating the degradation of pollutants. Figure 3(e) The XPS spectrum of Ols can be resolved into two peaks at 531.58 and 530.28 eV, corresponding to oxygen vacancies and lattice oxygen, respectively. In comparison with S 0.3 -Co@P2C, S 0.3 -Co@P2C 700 and S 0.3 -Co@P0C, the content of oxygen vacancies gradually increased with the introduction of PET and microwave treatment. The defects formed with the generation of oxygen vacancies can be regarded as electron donors, and appropriate oxygen vacancies can significantly improve the activation performance of metal catalysts for PMS.

[0023] Case 2 (reaction see Table 1, item 1, PMS degradation of CBZ)

[0024] The temperature of the constant temperature magnetic stirring water bath was set to 25 ℃, and the initial pH was adjusted to 6.6 with 1M sulfuric acid or sodium hydroxide. In a 100 mL round-bottom flask containing 50 mL CBZ (20 mg / L) aqueous solution, 0.5 g / L PMS was added to start the degradation reaction. 1 mL of reaction solution was extracted at predetermined time intervals, filtered with a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL methanol, and the concentration of carbamazepine was determined by ultraviolet-visible spectrophotometer (286 nm). It was found that the degradation rate of PMS to CBZ was 6.6% in 15 minutes, and the rate constant was 0.0058 min -1 .

[0025] Case 3 (reaction see Table 1, item 2, CoO catalyst degradation of CBZ)

[0026] The temperature of the constant temperature magnetic stirring water bath was set to 25 ℃, and the initial pH was adjusted to 6.6 with 1M sulfuric acid or sodium hydroxide. In a 100 mL round-bottom flask containing 50 mL CBZ (20 mg / L) aqueous solution, 0.5 g / L PMS was added to start the degradation reaction. 1 mL of reaction solution was extracted at predetermined time intervals, filtered with a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL methanol, and the concentration of carbamazepine was determined by ultraviolet-visible spectrophotometer (286 nm). It was found that the degradation rate of PMS to CBZ was 6.6% in 15 minutes, and the rate constant was 0.0058 min -1 .

[0027] Case 4 (reaction see Table 1, item 3, S@P2C 700 catalyst degradation of CBZ)

[0028] A constant temperature magnetic stirring water bath was set at 25 °C, and the initial pH was adjusted to 6.6 with 1 M sulfuric acid or sodium hydroxide. In a 100 mL round bottom flask containing 50 mL CBZ (20 mg / L) aqueous solution, 0.16 g / L of S@P2C 700 The degradation reaction was started with 0.5 g / L of PMS. At predetermined time intervals, 1 mL of the reaction solution was extracted, filtered using a 0.25 pm pore membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of CBZ was determined using a UV-Vis spectrophotometer (286 nm). It was found that S@P2C 700 The degradation rate of CBZ by the catalyst was 13.6%, and the rate constant was 0.0167 min -1 .

[0029] Case 5 (reaction see Table 1, entry 4, S 0.3 -Co@P2C 700 degradation of CBZ by the catalyst

[0030] A constant temperature magnetic stirring water bath was set at 25 °C, and the initial pH was adjusted to 6.6 with 1 M sulfuric acid or sodium hydroxide. In a 100 mL round bottom flask containing 50 mL CBZ (20 mg / L) aqueous solution, 0.16 g / L of S 0.3 -Co@P2C 700 The degradation reaction was started with 0.5 g / L of PMS. At predetermined time intervals, 1 mL of the reaction solution was extracted, filtered using a 0.25 pm pore membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of CBZ was determined using a UV-Vis spectrophotometer (286 nm). It was found that S 0.3 -Co@P2C 700 The degradation rate of CBZ by the catalyst was 82.1%, and the rate constant was 0.2147 min -1 .

[0031] Case 6 (reaction see Table 1, entry 5, S@P2C catalyst degradation of CBZ)

[0032] The temperature of the constant temperature magnetic stirring water bath was set to 25 °C, and the initial pH was adjusted to 6.6 with 1M sulfuric acid or sodium hydroxide. In a 100 mL round bottom flask containing 50 mL CBZ (20 mg / L) aqueous solution, 0.16 g / L of S@P2C catalyst and 0.5 g / L of PMS were added to start the degradation reaction. 1 mL of reaction solution was extracted at predetermined time intervals, filtered using a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of carbamazepine was determined using a UV-visible spectrophotometer (286 nm). It was found that the degradation rate of CBZ by S@P2C catalyst was 17.3% in 15 minutes, and the rate constant was 0.0087 min -1 .

[0033] Example 7 (reaction see Table 1, entry 6, degradation of CBZ by Co@P2C catalyst)

[0034] The temperature of the constant temperature magnetic stirring water bath was set to 25 °C, and the initial pH was adjusted to 6.6 with 1M sulfuric acid or sodium hydroxide. In a 100 mL round bottom flask containing 50 mL CBZ (20 mg / L) aqueous solution, 0.16 g / L of S@P2C catalyst and 0.5 g / L of PMS were added to start the degradation reaction. 1 mL of reaction solution was extracted at predetermined time intervals, filtered using a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of carbamazepine was determined using a UV-visible spectrophotometer (286 nm). It was found that the degradation rate of CBZ by S@P2C catalyst was 17.3% in 15 minutes, and the rate constant was 0.0087 min -1 .

[0035] Example 8 (reaction see Table 1, entry 7, degradation of CBZ by Co@P0C catalyst)

[0036] The temperature of the constant temperature magnetic stirring water bath was set to 25 °C, and the initial pH was adjusted to 6.6 with 1M sulfuric acid or sodium hydroxide. In a 100 mL round bottom flask containing 50 mL CBZ (20 mg / L) aqueous solution, 0.16 g / L of S@P2C catalyst and 0.5 g / L of PMS were added to start the degradation reaction. 1 mL of reaction solution was extracted at predetermined time intervals, filtered using a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of carbamazepine was determined using a UV-visible spectrophotometer (286 nm). It was found that the degradation rate of CBZ by S@P2C catalyst was 17.3% in 15 minutes, and the rate constant was 0.0087 min -1 .

[0037] Example 9 (reaction see Table 1, entry 8, degradation of CBZ by S 0.3Degradation of CBZ by Co@P0C catalyst

[0038] The temperature of the constant temperature magnetic stirring water bath was set to 25 ℃, and the initial pH was adjusted to 6.6 with 1M sulfuric acid or sodium hydroxide. 0.16 g / L of S 0.3 The degradation reaction was started by Co@P0C catalyst and 0.5 g / L of PMS. 1 mL of reaction solution was extracted at predetermined time intervals, filtered using a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of carbamazepine was determined using a UV-visible spectrophotometer (286 nm), and it was found that S 0.3 The degradation rate of CBZ by Co@P0C catalyst was 81.9%, and the rate constant was 0.2189 min -1 .

[0039] Case 10 (reaction see Table 1, entry 9, S 0.3 Degradation of CBZ by Co@P2C catalyst

[0040] The temperature of the constant temperature magnetic stirring water bath was set to 25 ℃, and the initial pH was adjusted to 6.6 with 1M sulfuric acid or sodium hydroxide. 0.16 g / L of S 0.3 The degradation reaction was started by Co@P2C catalyst and 0.5 g / L of PMS. 1 mL of reaction solution was extracted at predetermined time intervals, filtered using a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of carbamazepine was determined using a UV-visible spectrophotometer (286 nm), and it was found that S 0.3 The degradation rate of CBZ by Co@P2C catalyst was 100%, and the rate constant was 0.7445 min -1 .

[0041]

[0042] Case 11 (reaction see Table 2, entry 1, S 0.1 Degradation of CBZ by Co@P2C catalyst

[0043] The temperature of the constant temperature magnetic stirring water bath was set to 25 ℃, and the initial pH was adjusted to 6.6 with 1M sulfuric acid or sodium hydroxide. 0.16 g / L of S 0.1Co@P2C catalyst and 0.5 g / L of PMS. At predetermined time intervals, 1 mL of the reaction solution was extracted, filtered using a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of carbamazepine was determined using a UV-visible spectrophotometer (286 nm), finding that S 0.1 The degradation rate of CBZ by the Co@P2C catalyst was 69.3% and the rate constant was 0.0710 min -1 .

[0044] Case 12 (reaction see Table 2, entry 2, S 0.2 Degradation of CBZ by Co@P2C

[0045] The temperature of the thermostatic magnetic stirring water bath was set to 25 °C and the initial pH was adjusted to 6.6 with 1 M sulfuric acid or sodium hydroxide. In a 100 mL round-bottom flask containing 50 mL of an aqueous solution of CBZ (20 mg / L), 0.16 g / L of S 0.2 Co@P2C catalyst and 0.5 g / L of PMS. At predetermined time intervals, 1 mL of the reaction solution was extracted, filtered using a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of carbamazepine was determined using a UV-visible spectrophotometer (286 nm), finding that S 0.2 The degradation rate of CBZ by the Co@P2C catalyst was 77.2% and the rate constant was 0.1312 min -1 .

[0046] Case 13 (reaction see Table 2, entry 4, S 0.4 Degradation of CBZ by Co@P2C

[0047] The temperature of the thermostatic magnetic stirring water bath was set to 25 °C and the initial pH was adjusted to 6.6 with 1 M sulfuric acid or sodium hydroxide. In a 100 mL round-bottom flask containing 50 mL of an aqueous solution of CBZ (20 mg / L), 0.16 g / L of S 0.4 Co@P2C catalyst and 0.5 g / L of PMS. At predetermined time intervals, 1 mL of the reaction solution was extracted, filtered using a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of carbamazepine was determined using a UV-visible spectrophotometer (286 nm), finding that S 0.4 The degradation rate of CBZ by the Co@P2C catalyst was 86.3% and the rate constant was 0.3678 min -1 .

[0048] Case 14 (reaction see Table 2, entry 5, S 0.5 Degradation of CBZ by Co@P2C catalyst

[0049] The temperature of the constant temperature magnetic stirring water bath was set to 25 ℃, and the initial pH was adjusted to 6.6 with 1M sulfuric acid or sodium hydroxide. 0.16 g / L of S 0.5 The degradation reaction was started by adding Co@P2C catalyst and 0.5 g / L of PMS. 1 mL of reaction solution was extracted at predetermined time intervals, filtered using a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of carbamazepine was determined using a UV-visible spectrophotometer (286 nm), and it was found that S 0.5 The degradation rate of CBZ by Co@P2C catalyst was 78.3%, and the rate constant was 0.1402 min -1 .

[0050]

[0051] Case 15 (reaction see Table 3, entry 1, 0.12 g / L of S 0.3 Degradation of CBZ by Co@P2C catalyst

[0052] The temperature of the constant temperature magnetic stirring water bath was set to 25 ℃, and the initial pH was adjusted to 6.6 with 1M sulfuric acid or sodium hydroxide. 0.12 g / L of S 0.3 The degradation reaction was started by adding Co@P2C catalyst and 0.5 g / L of PMS. 1 mL of reaction solution was extracted at predetermined time intervals, filtered using a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of carbamazepine was determined using a UV-visible spectrophotometer (286 nm), and it was found that S 0.3 The degradation rate of CBZ by Co@P2C catalyst was 88.6%.

[0053] Case 15 (reaction see Table 3, entry 2, 0.14 g / L of S 0.3 Degradation of CBZ by Co@P2C catalyst

[0054] The temperature of the constant temperature magnetic stirring water bath was set to 25 ℃, and the initial pH was adjusted to 6.6 with 1M sulfuric acid or sodium hydroxide. 0.14 g / L of S 0.3The degradation reaction was started with Co@P2C catalyst and 0.5 g / L of PMS. At predetermined time intervals, 1 mL of the reaction solution was extracted, filtered using a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of carbamazepine was determined using a UV-visible spectrophotometer (286 nm), finding that S 0.3 The degradation rate of CBZ by the Co@P2C catalyst was 95.8%.

[0055] Case 15 of implementation (reaction see Table 3, entry 4, 0.18 g / L of S 0.3 The degradation of CBZ by the Co@P2C catalyst

[0056] The temperature of the thermostatic magnetic stirring water bath was set to 25 °C and the initial pH was adjusted to 6.6 with 1 M sulfuric acid or sodium hydroxide. In a 100 mL round-bottom flask containing 50 mL of an aqueous solution of CBZ (20 mg / L), 0.18 g / L of S 0.3 The degradation reaction was started with Co@P2C catalyst and 0.5 g / L of PMS. At predetermined time intervals, 1 mL of the reaction solution was extracted, filtered using a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of carbamazepine was determined using a UV-visible spectrophotometer (286 nm), finding that S 0.3 The degradation rate of CBZ by the Co@P2C catalyst was 98.7%.

[0057]

[0058] Case 16 of implementation (reaction see Table 4, entry 1, effect of 0.2 g / L of PMS on the degradation of CBZ)

[0059] The temperature of the thermostatic magnetic stirring water bath was set to 25 °C and the initial pH was adjusted to 6.6 with 1 M sulfuric acid or sodium hydroxide. In a 100 mL round-bottom flask containing 50 mL of an aqueous solution of CBZ (20 mg / L), 0.16 g / L of S 0.3 The degradation reaction was started with Co@P2C catalyst and 0.2 g / L of PMS. At predetermined time intervals, 1 mL of the reaction solution was extracted, filtered using a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of carbamazepine was determined using a UV-visible spectrophotometer (286 nm), finding that S 0.3 The degradation rate of CBZ by the Co@P2C catalyst was 82.1%.

[0060] Case 17 of implementation (reaction see Table 4, entry 2, effect of 0.3 g / L of PMS on the degradation of CBZ)

[0061] The temperature of the thermostatic magnetic stirring water bath was set to 25 °C and the initial pH was adjusted to 6.6 with 1 M sulfuric acid or sodium hydroxide. In a 100 mL round bottom flask containing 50 mL of CBZ (20 mg / L) aqueous solution, 0.16 g / L of S 0.3 The degradation reaction was started with 0.3 g / L of PMS and Co@P2C catalyst. At predetermined time intervals, 1 mL of the reaction solution was extracted, filtered using a 0.25 pm pore membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of carbamazepine was determined using a UV-Vis spectrophotometer (286 nm), finding that in 15 minutes S 0.3 The degradation rate of CBZ with Co@P2C catalyst was 90.3%.

[0062] Case 18 (reaction see Table 4, entry 3, effect of 0.4 g / L of PMS on CBZ degradation)

[0063] The temperature of the thermostatic magnetic stirring water bath was set to 25 °C and the initial pH was adjusted to 6.6 with 1 M sulfuric acid or sodium hydroxide. In a 100 mL round bottom flask containing 50 mL of CBZ (20 mg / L) aqueous solution, 0.16 g / L of S 0.3 The degradation reaction was started with 0.4 g / L of PMS and Co@P2C catalyst. At predetermined time intervals, 1 mL of the reaction solution was extracted, filtered using a 0.25 pm pore membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of carbamazepine was determined using a UV-Vis spectrophotometer (286 nm), finding that in 15 minutes S 0.3 The degradation rate of CBZ with Co@P2C catalyst was 98.6%.

[0064] Case 19 (reaction see Table 4, entry 5, effect of 0.6 g / L of PMS on CBZ degradation)

[0065] The temperature of the thermostatic magnetic stirring water bath was set to 25 °C and the initial pH was adjusted to 6.6 with 1 M sulfuric acid or sodium hydroxide. In a 100 mL round bottom flask containing 50 mL of CBZ (20 mg / L) aqueous solution, 0.16 g / L of S 0.3 The degradation reaction was started with 0.6 g / L of PMS and Co@P2C catalyst. At predetermined time intervals, 1 mL of the reaction solution was extracted, filtered using a 0.25 pm pore membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of carbamazepine was determined using a UV-Vis spectrophotometer (286 nm), finding that in 15 minutes S 0.3 The degradation rate of CBZ with Co@P2C catalyst was 84.3%.

[0066]

[0067] Case 20 (reaction see Table 5, entry 1, S 0.3 -Co@P2C catalyst degradation of CBZ

[0068] The temperature of the constant temperature magnetic stirring water bath was set to 25 °C, and the initial pH was adjusted to 3 with 1 M sulfuric acid or sodium hydroxide. 0.16 g / L of S 0.3 -Co@P2C catalyst and 0.5 g / L of PMS to start the degradation reaction. 1 mL of reaction solution was extracted at predetermined time intervals, filtered using a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of carbamazepine was determined using a UV-visible spectrophotometer (286 nm), and it was found that S 0.3 The degradation rate of CBZ by the -Co@P2C catalyst was 77.6%.

[0069] Case 21 (reaction see Table 5, entry 2, S 0.3 -Co@P2C catalyst degradation of CBZ

[0070] The temperature of the constant temperature magnetic stirring water bath was set to 25 °C, and the initial pH was adjusted to 5 with 1 M sulfuric acid or sodium hydroxide. 0.16 g / L of S 0.3 -Co@P2C catalyst and 0.5 g / L of PMS to start the degradation reaction. 1 mL of reaction solution was extracted at predetermined time intervals, filtered using a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of carbamazepine was determined using a UV-visible spectrophotometer (286 nm), and it was found that S 0.3 The degradation rate of CBZ by the -Co@P2C catalyst was 90.5%.

[0071] Case 22 (reaction see Table 5, entry 4, S 0.3 -Co@P2C catalyst degradation of CBZ

[0072] The temperature of the constant temperature magnetic stirring water bath was set to 25 °C, and the initial pH was adjusted to 7 with 1 M sulfuric acid or sodium hydroxide. 0.16 g / L of S 0.3The degradation reaction was started with Co@P2C catalyst and 0.5 g / L of PMS. At predetermined time intervals, 1 mL of the reaction solution was extracted, filtered using a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of carbamazepine was determined using a UV-visible spectrophotometer (286 nm), finding that S 0.3 The degradation rate of CBZ by the Co@P2C catalyst was 99.2%.

[0073] Example 23 (reaction see Table 5, entry 5, S 0.3 Degradation of CBZ by the Co@P2C catalyst

[0074] The temperature of the thermostatic magnetic stirring water bath was set to 25 °C and the initial pH was adjusted to 9 using 1 M sulfuric acid or sodium hydroxide. In a 100 mL round-bottom flask containing 50 mL of an aqueous solution of CBZ (20 mg / L), 0.16 g / L of S 0.3 The degradation reaction was started with Co@P2C catalyst and 0.5 g / L of PMS. At predetermined time intervals, 1 mL of the reaction solution was extracted, filtered using a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of carbamazepine was determined using a UV-visible spectrophotometer (286 nm), finding that S 0.3 The degradation rate of CBZ by the Co@P2C catalyst was 89.1%.

[0075] Example 24 (reaction see Table 5, entry 6, S 0.3 Degradation of CBZ by the Co@P2C catalyst

[0076] The temperature of the thermostatic magnetic stirring water bath was set to 25 °C and the initial pH was adjusted to 11 using 1 M sulfuric acid or sodium hydroxide. In a 100 mL round-bottom flask containing 50 mL of an aqueous solution of CBZ (20 mg / L), 0.16 g / L of S 0.3 The degradation reaction was started with Co@P2C catalyst and 0.5 g / L of PMS. At predetermined time intervals, 1 mL of the reaction solution was extracted, filtered using a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of carbamazepine was determined using a UV-visible spectrophotometer (286 nm), finding that S 0.3 The degradation rate of CBZ by the Co@P2C catalyst was 81.1%.

[0077]

[0078] Example 25 (reaction see Table 6, entry 1, S 0.3Degradation of CBZ by Co@P2C catalyst

[0079] The temperature of the constant temperature magnetic stirring water bath was set to 15℃, and the initial pH was adjusted to 6.6 with 1M sulfuric acid or sodium hydroxide. 0.16 g / L of S 0.3 The degradation reaction was started by Co@P2C catalyst and 0.5 g / L of PMS. 1 mL of reaction solution was extracted at predetermined time intervals, filtered using a 0.25 µm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of carbamazepine was determined using a UV-visible spectrophotometer (286 nm), and it was found that S 0.3 The degradation rate of CBZ by Co@P2C catalyst was 97.6%, and the rate constant was 0. 2836min -1 .

[0080] Case 26 (reaction see Table 6, entry 2, S 0.3 Degradation of CBZ by Co@P2C catalyst

[0081] The temperature of the constant temperature magnetic stirring water bath was set to 20℃, and the initial pH was adjusted to 6.6 with 1M sulfuric acid or sodium hydroxide. 0.16 g / L of S 0.3 The degradation reaction was started by Co@P2C catalyst and 0.5 g / L of PMS. 1 mL of reaction solution was extracted at predetermined time intervals, filtered using a 0.25 µm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of carbamazepine was determined using a UV-visible spectrophotometer (286 nm), and it was found that S 0.3 The degradation rate of CBZ by Co@P2C catalyst was 98.7%, and the rate constant was 0. 3210min -1 .

[0082] Case 27 (reaction see Table 6, entry 4, S 0.3 Degradation of CBZ by Co@P2C catalyst

[0083] The temperature of the constant temperature magnetic stirring water bath was set to 30℃, and the initial pH was adjusted to 6.6 with 1M sulfuric acid or sodium hydroxide. 0.16 g / L of S 0.3Co@P2C catalyst and 0.5 g / L of PMS. At predetermined time intervals, 1 mL of the reaction solution was extracted, filtered using a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of carbamazepine was determined using a UV-Vis spectrophotometer (286 nm), finding that S 0.3 The degradation rate of CBZ by the Co@P2C catalyst was 100% and the rate constant was 0.8597 min -1 .

[0084]

[0085] Example 28 (reaction see Table 7, entry 2, 2 mM of Cl - in the presence of the Co@P2C catalyst on the degradation of CBZ)

[0086] The temperature of the thermostatic magnetic stirring water bath was set to 25 °C and the initial pH was adjusted to 6.6 with 1 M sulfuric acid or sodium hydroxide. In a 100 mL round-bottom flask containing 50 mL of an aqueous solution of CBZ (20 mg / L), 0.16 g / L of S 0.3 -Co@P2C catalyst, 2 mM of Cl - solution and 0.5 g / L of PMS. At predetermined time intervals, 1 mL of the reaction solution was extracted, filtered using a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of carbamazepine was determined using a UV-Vis spectrophotometer (286 nm), finding that S 0.3 The degradation rate of CBZ by the Co@P2C catalyst was 82.7%.

[0087] Example 29 (reaction see Table 7, entry 3, 5 mM of Cl - in the presence of the Co@P2C catalyst on the degradation of CBZ)

[0088] The temperature of the thermostatic magnetic stirring water bath was set to 25 °C and the initial pH was adjusted to 6.6 with 1 M sulfuric acid or sodium hydroxide. In a 100 mL round-bottom flask containing 50 mL of an aqueous solution of CBZ (20 mg / L), 0.16 g / L of S 0.3 -Co@P2C catalyst, 5 mM of Cl - solution and 0.5 g / L of PMS. At predetermined time intervals, 1 mL of the reaction solution was extracted, filtered using a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of carbamazepine was determined using a UV-Vis spectrophotometer (286 nm), finding that S 0.3 The degradation rate of CBZ by the Co@P2C catalyst was 80.2%.

[0089] Example 30 (reaction see Table 7, entry 4, 10 mM of Cl - Effect on CBZ degradation in the presence of)

[0090] The temperature of the constant temperature magnetic stirring water bath was set to 25 ℃, and the initial pH was adjusted to 6.6 with 1M sulfuric acid or sodium hydroxide. In a 100 mL round-bottom flask containing 50 mL of CBZ (20 mg / L) aqueous solution, 0.16 g / L of S 0.3 -Co@P2C catalyst, 10 mM of Cl - solution and 0.5 g / L of PMS to start the degradation reaction. At predetermined time intervals, 1 mL of the reaction solution was extracted, filtered using a 0.25 μm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of carbamazepine was determined using a UV-visible spectrophotometer (286 nm), and it was found that S 0.3 The degradation rate of CBZ by the -Co@P2C catalyst was 79.8%.

[0091]

[0092] Example 31 (reaction see Table 8, entry 2, 2 mM of NO3 − Effect on CBZ degradation in the presence of)

[0093] The temperature of the constant temperature magnetic stirring water bath was set to 25 ℃, and the initial pH was adjusted to 6.6 with 1M sulfuric acid or sodium hydroxide. In a 100 mL round-bottom flask containing 50 mL of CBZ (20 mg / L) aqueous solution, 0.16 g / L of S 0.3 -Co@P2C catalyst, 2 mM of NO3 − solution and 0.5 g / L of PMS to start the degradation reaction. At predetermined time intervals, 1 mL of the reaction solution was extracted, filtered using a 0.25 μm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of carbamazepine was determined using a UV-visible spectrophotometer (286 nm), and it was found that S 0.3 The degradation rate of CBZ by the -Co@P2C catalyst was 83.4%.

[0094] Example 32 (reaction see Table 8, entry 3, 5 mM of NO3 − Effect on CBZ degradation in the presence of)

[0095] A constant temperature magnetic stirring water bath was set at 25 °C, and the initial pH was adjusted to 6.6 with 1 M sulfuric acid or sodium hydroxide. In a 100 mL round-bottom flask containing 50 mL of CBZ (20 mg / L) aqueous solution, 0.16 g / L of S 0.3 -Co@P2C catalyst, 5 mM of NO3 − solution, and 0.5 g / L of PMS was added to start the degradation reaction. At predetermined time intervals, 1 mL of the reaction solution was extracted, filtered using a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of CBZ was determined using a UV-Vis spectrophotometer (286 nm). It was found that S 0.3 -Co@P2C catalyst had a degradation rate of 81.7% for CBZ.

[0096] Case 33 (reaction see Table 8, entry 4, 10 mM of NO3 − effect on the degradation of CBZ)

[0097] A constant temperature magnetic stirring water bath was set at 25 °C, and the initial pH was adjusted to 6.6 with 1 M sulfuric acid or sodium hydroxide. In a 100 mL round-bottom flask containing 50 mL of CBZ (20 mg / L) aqueous solution, 0.16 g / L of S 0.3 -Co@P2C catalyst, 10 mM of NO3 − solution, and 0.5 g / L of PMS was added to start the degradation reaction. At predetermined time intervals, 1 mL of the reaction solution was extracted, filtered using a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of CBZ was determined using a UV-Vis spectrophotometer (286 nm). It was found that S 0.3 -Co@P2C catalyst had a degradation rate of 78.6% for CBZ.

[0098]

[0099] Case 34 (reaction see Table 9, entry 2, 2 mM of H2PO4 - effect on the degradation of CBZ)

[0100] A constant temperature magnetic stirring water bath was set at 25 °C, and the initial pH was adjusted to 6.6 with 1 M sulfuric acid or sodium hydroxide. In a 100 mL round-bottom flask containing 50 mL of CBZ (20 mg / L) aqueous solution, 0.16 g / L of S 0.3 -Co@P2C catalyst, 2 mM of H2PO4 -The degradation reaction was started with 0.5 g / L of PMS. At predetermined time intervals, 1 mL of the reaction solution was extracted, filtered using a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of carbamazepine was determined using a UV-visible spectrophotometer (286 nm), finding that S 0.3 The degradation rate of CBZ by the Co@P2C catalyst was 89.8%.

[0101] Case 35 (reaction see Table 9, entry 3, 5 mM of H2PO4 - Effect on the degradation of CBZ in the presence of)

[0102] The temperature of the thermostatic magnetic stirring water bath was set to 25 °C and the initial pH was adjusted to 6.6 with 1 M sulfuric acid or sodium hydroxide. In a 100 mL round-bottom flask containing 50 mL of an aqueous solution of CBZ (20 mg / L), 0.16 g / L of S 0.3 Co@P2C catalyst, 5 mM of H2PO4 - The degradation reaction was started with 0.5 g / L of PMS. At predetermined time intervals, 1 mL of the reaction solution was extracted, filtered using a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of carbamazepine was determined using a UV-visible spectrophotometer (286 nm), finding that S 0.3 The degradation rate of CBZ by the Co@P2C catalyst was 89.4%.

[0103] Case 36 (reaction see Table 9, entry 4, 10 mM of H2PO4 - Effect on the degradation of CBZ in the presence of)

[0104] The temperature of the thermostatic magnetic stirring water bath was set to 25 °C and the initial pH was adjusted to 6.6 with 1 M sulfuric acid or sodium hydroxide. In a 100 mL round-bottom flask containing 50 mL of an aqueous solution of CBZ (20 mg / L), 0.16 g / L of S 0.3 Co@P2C catalyst, 10 mM of H2PO4 - The degradation reaction was started with 0.5 g / L of PMS. At predetermined time intervals, 1 mL of the reaction solution was extracted, filtered using a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of carbamazepine was determined using a UV-visible spectrophotometer (286 nm), finding that S 0.3 The degradation rate of CBZ by the Co@P2C catalyst was 84.5%.

[0105]

[0106] Case 37 (reaction see Table 10, entry 2, effect of 5 mg / L of HA on CBZ degradation)

[0107] The temperature of the constant temperature magnetic stirring water bath was set to 25 °C, and the initial pH was adjusted to 6.6 with 1M sulfuric acid or sodium hydroxide. 0.16 g / L of S 0.3 The degradation reaction was started with Co@P2C catalyst, 5 mg / L of HA solution and 0.5 g / L of PMS. 1 mL of reaction solution was extracted at predetermined time intervals, filtered using a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of carbamazepine was determined using a UV-visible spectrophotometer (286 nm), and it was found that S 0.3 The degradation rate of CBZ by Co@P2C catalyst was 84.9%.

[0108] Case 38 (reaction see Table 10, entry 3, effect of 10 mg / L of HA on CBZ degradation)

[0109] The temperature of the constant temperature magnetic stirring water bath was set to 25 °C, and the initial pH was adjusted to 6.6 with 1M sulfuric acid or sodium hydroxide. 0.16 g / L of S 0.3 The degradation reaction was started with Co@P2C catalyst, 10 mg / L of HA solution and 0.5 g / L of PMS. 1 mL of reaction solution was extracted at predetermined time intervals, filtered using a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of carbamazepine was determined using a UV-visible spectrophotometer (286 nm), and it was found that S 0.3 The degradation rate of CBZ by Co@P2C catalyst was 76.2%.

[0110] Case 39 (reaction see Table 10, entry 4, effect of 15 mg / L of HA on CBZ degradation)

[0111] The temperature of the constant temperature magnetic stirring water bath was set to 25 °C, and the initial pH was adjusted to 6.6 with 1M sulfuric acid or sodium hydroxide. 0.16 g / L of S 0.3Co@P2C catalyst, 15 mg / L of HA solution and 0.5 g / L of PMS started the degradation reaction. At predetermined time intervals, 1 mL of the reaction solution was extracted, filtered using a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of CBZ was determined using a UV- visible spectrophotometer (286 nm), and it was found that S 0.3 The degradation rate of CBZ by the Co@P2C catalyst was 67.3%.

[0112]

[0113] Case 40 (reaction see Table 11, entries 1-5)

[0114] To evaluate the S 0.3 To evaluate the stability of the Co@P2C catalyst, 5 cycles were performed, and after each run, the resulting sample was collected by filtration, washing, and vacuum drying overnight, and the obtained solid was used for the next cycle. The temperature of the thermostatic magnetic stirring water bath was set to 25 °C, and the initial pH was adjusted to 6.6 with 1 M sulfuric acid or sodium hydroxide. In a 100 mL round-bottom flask containing 50 mL of CBZ (20 mg / L) aqueous solution, 0.16 g / L of S 0.3 The degradation rate of CBZ by the Co@P2C catalyst was 67.3%. 0.3 The degradation rate of CBZ by the Co@P2C catalyst was 100%, which remained above 90% in the first three cycles, 82.5% in the 4th cycle, and 80.6% in the 5th cycle.

[0115]

[0116] Case 41 (reaction see Table 12, entry 1, S 0.3 Degradation of methyl orange (MO) by the Co@P2C catalyst

[0117] The temperature of the thermostatic magnetic stirring water bath was set to 25 °C, and the initial pH was adjusted to 6.6 with 1 M sulfuric acid or sodium hydroxide. In a 100 mL round-bottom flask containing 50 mL of MO (20 mg / L) aqueous solution, 0.16 g / L of S 0.3The degradation reaction was started with Co@P2C catalyst and 0.5 g / L of PMS. At predetermined time intervals, 1 mL of the reaction solution was extracted, filtered using a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of MO was determined using a UV-visible spectrophotometer (463 nm), finding that S 0.3 The degradation rate of CBZ by the Co@P2C catalyst was 100 %.

[0118] Case 42 (reaction see Table 12, entry 2, S 0.3 Degradation of tetracycline hydrochloride (TC) by the Co@P2C catalyst

[0119] The temperature of the thermostatic magnetic stirring water bath was set to 25 °C and the initial pH was adjusted to 6.6 with 1 M sulfuric acid or sodium hydroxide. In a 100 mL round-bottom flask containing 50 mL of an aqueous solution of TC (20 mg / L), 0.16 g / L of S 0.3 The degradation reaction was started with Co@P2C catalyst and 0.5 g / L of PMS. At predetermined time intervals, 1 mL of the reaction solution was extracted, filtered using a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of TC was determined using a UV-visible spectrophotometer (357 nm), finding that S 0.3 The degradation rate of TC by the Co@P2C catalyst was 100 %.

[0120] Case 43 (reaction see Table 12, entry 3, S 0.3 Degradation of oxytetracycline hydrochloride (OTC) by the Co@P2C catalyst

[0121] The temperature of the thermostatic magnetic stirring water bath was set to 25 °C and the initial pH was adjusted to 6.6 with 1 M sulfuric acid or sodium hydroxide. In a 100 mL round-bottom flask containing 50 mL of an aqueous solution of OTC (20 mg / L), 0.16 g / L of S 0.3 The degradation reaction was started with Co@P2C catalyst and 0.5 g / L of PMS. At predetermined time intervals, 1 mL of the reaction solution was extracted, filtered using a 0.25 pm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of OTC was determined using a UV-visible spectrophotometer (352 nm), finding that S 0.3 The degradation rate of OTC by the Co@P2C catalyst was 100 %.

[0122] Case 44 (reaction see Table 12, entry 4, S 0.3 Degradation of ciprofloxacin (CIP) by the Co@P2C catalyst

[0123] The temperature of the constant temperature magnetic stirring water bath was set to 25 ℃, and the initial pH was adjusted to 6.6 with 1M sulfuric acid or sodium hydroxide. 0.16 g / L of S 0.3 -Co@P2C catalyst and 0.5 g / L of PMS started the degradation reaction. 1 mL of reaction solution was extracted at predetermined time intervals, filtered using a 0.25µm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of CIP was determined using a UV-visible spectrophotometer (278 nm), and it was found that S 0.3 The degradation rate of CIP by the -Co@P2C catalyst was 93.9 %.

[0124] Case 45 (reaction, see Table 12, entry 5, S 0.3 -Co@P2C catalyst for Rhodamine B (RhB) degradation

[0125] The temperature of the constant temperature magnetic stirring water bath was set to 25 ℃, and the initial pH was adjusted to 6.6 with 1M sulfuric acid or sodium hydroxide. 0.16 g / L of S 0.3 -Co@P2C catalyst and 0.5 g / L of PMS started the degradation reaction. 1 mL of reaction solution was extracted at predetermined time intervals, filtered using a 0.25µm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of CIP was determined using a UV-visible spectrophotometer (278 nm), and it was found that S 0.3 The degradation rate of CIP by the -Co@P2C catalyst was 93.9 %.

[0126]

[0127] Case 46 (reaction, see Table 13, effect of different quenching agents on CBZ degradation)

[0128] Methanol (MeOH) and tert-butyl alcohol (TBA) are commonly used as free radical quenchers. MeOH can quench SO4 •- and ·OH, TBA can quench ·OH, and p-benzoquinone (BQ) and curcumin (Cur) can quench O2 •- and 1 O2, respectively. The temperature of the constant temperature magnetic stirring water bath was set to 25 ℃, and the initial pH was adjusted to 6.6 with 1M sulfuric acid or sodium hydroxide. 0.16 g / L of S 0.3The degradation reaction was initiated by adding Co@P2C catalyst and excess quencher, followed by 0.5 g / L PMS to the reactor. At predetermined time intervals, 1 mL of the reaction solution was extracted, filtered through a 0.25 µm microporous membrane, and squeezed into centrifuge tubes containing 2 mL of methanol. The concentration of the CBZ solution was then detected at 286 nm using a UV-Vis spectrophotometer. It was found that under the quenching effects of MeOH, TBA, BQ, and Cur, S... 0.3 The degradation rates of CBZ by the -Co@P2C catalysts were 27.2%, 78.4%, 66.9%, and 86.6%, respectively. Quenching results showed that all quenchers had a significant effect on S... 0.3 The -Co@P2C / PMS system exhibits a certain inhibitory effect on the degradation of CBZ, indicating that the S-type plastics prepared by microwave pyrolysis of waste plastics... 0.3 -Co@P2C catalytic material generated SO4 during the activation of PMS. •- ·OH, O2 •- and 1 O2. Compared to ·OH, SO4 •- Free radicals in S 0.3 -Co@P2C / PMS system contributes more significantly to CBZ degradation; and 1 Compared to O2, O2 •- It makes a more significant contribution to the removal of CBZ. Overall, S 0.3 The -Co@P2C / PMS system involves both radical and non-radical pathways, including SO4. •- and O2 •- Plays a major role, and 1 O2 and ·OH play a secondary role in the degradation of CBZ.

[0129]

Claims

1. Use of a porous carbon material catalyst prepared by microwave carbonization of waste plastics in the degradation of organic pollutants, characterized in that: A simple microwave pyrolysis method was used to synthesize a waste plastic derived carbon material catalyst with a porous morphology from waste plastic polyethylene terephthalate (PET) as raw material, cobalt nitrate as microwave absorber and catalytic activation center, alpha-cellulose as carbonization auxiliary agent, and thiourea as metal sulfuration reagent in a microwave oven with a power of 800 W for 10 min of pyrolysis; The preparation steps of the porous carbon material catalyst are as follows: 0.230 g of PET powder, 0.230 g of alpha-cellulose, and 0.230 g of thiourea were weighed and mixed with 10 mL of deionized water to form a mixture, and then the mixture was placed in a microwave oven with a power of 800 W for 10 min of pyrolysis to obtain the porous carbon material catalyst. Co(N03)2-6H20, 0.115 g of a-cellulose powder and thiourea were mixed homogeneously in a ceramic mortar and the mixture was placed in a 25 mL crucible and pyrolyzed in a commercial microwave oven at 800 W for 10 min. After the material was cooled, it was washed with water / ethanol and dried in vacuum to obtain the porous carbon catalytic material; when the dose of thiourea was 0.1, 0.2, 0.3, 0.4 and 0.5 mmol, respectively, the prepared catalysts were named S x - Co@P2C, x = 0.1, 0.2, 0.3, 0.4, 0.5; The reaction of catalyst activation peroxymonosulfate (PMS) degrading organic pollutants: the temperature was controlled by a constant temperature magnetic stirring water bath, the initial pH was adjusted by 1M sulfuric acid or sodium hydroxide, and the degradation process was started by adding a catalyst with a set concentration and PMS in a 100 mL round-bottom flask containing 50 mL of an organic pollutant aqueous solution with a concentration of 20 mg / L; 1 mL of reaction solution was extracted at predetermined time intervals, filtered using a 0.25 μm microporous membrane, squeezed into a centrifuge tube containing 2 mL of methanol, and the concentration of organic pollutants was determined using a UV-visible spectrophotometer.

2. Use of a porous carbon material catalyst prepared from microwave carbonized waste plastics according to claim 1 in the degradation of organic pollutants, characterized in that: The catalyst preparation process is simple and short in preparation time, and the optimal catalyst exhibits obvious porous morphology structure characteristics; compared with traditional pyrolysis methods, microwave treatment and the introduction of PET are beneficial to the formation of cobalt oxide, cobalt sulfide, C=O, and oxygen vacancies and to the expansion of the specific surface area of the catalytic material.

3. Use of a porous carbon material catalyst prepared from microwave carbonized waste plastics according to claim 1 in the degradation of organic pollutants, characterized in that: The prepared porous carbon material catalyst S 0.3 -Co@P2C has high degradation efficiency on organic pollutants, and the removal rate of carbamazepine can reach 100.0% within 15 min, and the rate constant can reach 0.7445 min -1 ; the removal rates of p-methyl orange, tetracycline hydrochloride, oxytetracycline hydrochloride, ciprofloxacin and rhodamine B pollutants can all reach 100%, 100%, 100%, 93.9% and 98.6%, which proves that S 0.3 -Co@P2C / PMS catalytic system has good degradation capacity on different organic pollutants.

4. Use of a porous carbon material catalyst prepared from microwave carbonized waste plastics according to claim 1 in the degradation of organic pollutants, characterized in that: In S 0.3 In the Co@P2C / PMS catalytic system, PMS is catalytically activated to generate SO4 ·- , ·OH, O2 ·- and 1 O2, wherein SO4 ·- and O2 ·- are the main active substances for pollutant degradation, 1 O2 and ·OH are the secondary active substances.

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