Application of porous carbon catalyst for waste plastic microwave pyrolysis and activated PMS for degradation of organic pollutants

Abstract

The application discloses a kind of active site adjustable porous carbon catalyst based on waste plastics microwave pyrolysis preparation and its application in efficient activation peroxymonosulfate (PMS) degradation organic pollutants. The method is that polycarbonate (PC) is mixed with polypropylene (PP) or polyether sulfone (PES) waste plastics as carbon source, sodium hydroxide is used as microwave absorber and pore-forming agent, and microwave one-pot solid-phase pyrolysis method is used to prepare metal-free porous carbon catalyst (PC1PP3 and PC1PES3) under 800W power irradiation for 2 minutes. The application realizes directional switching of catalytic mechanism by regulating waste plastic components: doping PP significantly improves the graphitization degree, specific surface area (up to 934.99m 2 / g) and defect vacancy concentration of the material, and constructs a direct electron transfer channel; doping PES introduces thiophene sulfur sites and modifies the electronic structure of C=O sites, which promotes the generation of singlet oxygen ( 1 O2). The obtained catalyst shows excellent sulfamethoxazole (SMX) degradation performance in PMS activation system, and the highest reaction rate constant can reach 0.257min −1 . Moreover, PC1PP3 / PMS system realizes PMS utilization rate up to 92.5%. The application not only realizes high-value utilization of waste plastics, but also provides a new way for low-consumption drug and high-efficiency water treatment technology.

Description

Technical Field

[0001] This invention relates to porous carbon catalysts for microwave pyrolysis of waste plastics and their application in the degradation of organic pollutants by activated PMS. Background Technology

[0002] With the development of industrialization and modern medicine, the problem of persistent organic pollutants (especially antibiotics such as sulfamethoxazole and tetracycline) in aquatic environments is becoming increasingly serious. These pollutants not only disrupt the ecological balance but may also induce the spread of resistance genes, threatening human health. Traditional physical adsorption or biological treatment technologies are insufficient to completely remove these persistent pollutants. Advanced oxidation technologies (AOPs) based on peroxymonosulfate (PMS) have attracted much attention due to their strong oxidation capacity and fast reaction rate. Among them, heterogeneous carbon-based catalysts have become ideal materials for activating PMS due to their advantages such as no metal ion dissolution, environmental friendliness, tunable structure, and easy recovery.

[0003] Meanwhile, waste plastic disposal has become a global environmental crisis. Traditional landfill and incineration not only waste resources but also produce greenhouse gases and toxic byproducts. Carbonizing waste plastics into high-value-added carbon catalytic materials to achieve "waste-to-waste treatment" is currently a hot topic in solid waste resource utilization. However, existing technologies for the preparation and application of waste plastic-derived carbon materials still face the following significant problems: 1. High energy consumption and long cycle in the preparation process: Traditional carbon material preparation mostly relies on high-temperature pyrolysis in tube furnaces, which has a slow heating rate, long time consumption and huge energy consumption. Although microwave pyrolysis technology has the advantages of fast heating speed and uniform heating, common waste plastics (such as polypropylene PP and polyethersulfone PES) have weak microwave absorption capacity, making it difficult to achieve efficient carbonization directly. Usually, complex pretreatment or the addition of a large amount of expensive absorbent is required.

[0004] 2. Low PMS utilization efficiency (PUE): The activation mechanism of most current carbon catalysts for PMS mainly relies on the generation of highly reactive free radicals (such as sulfate radicals SO4). •- And hydroxyl radicals (•OH). Although these free radicals have strong oxidizing power, they readily react with background ions widely present in actual water bodies (such as Cl-). − CO3 2− HCO3 − The PMS may undergo ineffective reactions, either due to oxidation or natural organic matter, resulting in non-productive decomposition. It has been reported that the PMS utilization rate in most systems is typically below 40%, leading to significant waste of oxidants and increased treatment costs.

[0005] 3. Difficulty in regulating active sites: To overcome the limitations of free radical pathways, non-free radical pathways (such as singlet oxygen) are used. 1O2 or direct electron transfer has an advantage due to its strong anti-interference ability. However, how to accurately construct specific active sites (such as defect sites or specific heteroatom doping) in waste plastic-derived carbon materials through simple methods to achieve the switch of catalytic mechanism from inefficient free radical pathway to efficient non-free radical pathway remains a major challenge.

[0006] Therefore, developing a waste plastic-derived porous carbon catalyst with a simple process, low energy consumption, and high efficiency in non-radical activation of PMS through component control is of great significance for promoting the resource utilization of waste plastics and the development of low-cost water treatment technologies. Against this backdrop, this invention utilizes polycarbonate (PC)-assisted microwave co-pyrolysis of difficult-to-carbonize plastics (PP / PES) to successfully prepare a highly efficient catalyst with customized active sites. Summary of the Invention

[0007] This invention uses waste polycarbonate (PC) as the basic carbon source, waste polypropylene (PP) or polyethersulfone (PES) as modifiers, and sodium hydroxide (NaOH) as a microwave absorber and pore-forming agent. All solids are mixed uniformly in a mortar and pestle, followed by simple microwave-assisted pyrolysis for 2 minutes to prepare a metal-free porous carbon catalyst with tunable active sites. The catalyst preparation method in this invention is simple, the preparation time is extremely short, the catalyst can effectively activate PMS for the degradation of organic pollutants, and it has extremely high power efficiency (PUE).

[0008] This invention discloses a porous carbon catalyst for microwave pyrolysis of waste plastics and its application in degrading organic pollutants by activating PMS. The key feature is that a simple microwave-assisted one-pot solid-phase pyrolysis method is used, with waste plastic polycarbonate (PC) as a microwave absorption aid, polypropylene (PP) or polyether sulfone (PES) as a structure and site regulation component, and sodium hydroxide as an activator. The catalyst is rapidly synthesized in an 800W microwave oven for 2 minutes, using waste plastic-derived carbon materials with specific porous morphology and electronic structure. The preparation steps of the above porous carbon material catalyst are as follows: 1.5g of plastic powder mixture, which has been thoroughly ground into a uniform powder, is mixed with 0.5g of sodium hydroxide, placed in a 25mL crucible, and pyrolyzed at 800W microwave power for 2 minutes to obtain the porous carbon precursor PC. x PP y or PC x PES yWhere x:y represents the mass ratio of PC to PP and PC to PES, with values ​​of 2:1, 1:1, 1:2, 1:3, and 1:4, respectively. The precursor is then repeatedly washed with deionized water until the pH of the washing solution is neutral, and then vacuum dried at 60°C for 12 hours to obtain the final porous carbon catalyst material. When the mass ratio of PC to regulator (PP or PES) in the waste plastic is 2:1, 1:1, 1:2, 1:3, and 1:4, the prepared catalyst is named PC, respectively. x PP y and PC x PES y (x:y corresponds to the mass ratio); the preferred mass ratio is 1:3, and the catalysts prepared under this condition are named PC1PP3 (with a sponge-like porous structure and internal carbon vesicles) and PC1PES3 (with a coral-like three-dimensional interconnected network). The reaction of catalyst-activated peroxymonosulfate (PMS) for the degradation of organic pollutants: The temperature was controlled in a thermostatically heated magnetically stirred water bath. The initial pH was adjusted with 0.1M HCl / NaOH. The catalyst (0.16 g / L) and PMS (0.3-0.7 g / L) at predetermined concentrations were added to a 100 mL round-bottom flask containing 50 mL of an aqueous solution of organic pollutants (such as sulfamethoxazole, 10 mg / L) to start the degradation process. 1.5 mL of the reaction solution was extracted at predetermined time intervals, filtered through a 0.22 µm microporous membrane, squeezed into a centrifuge tube containing 1 mL of methanol, and the concentration of organic pollutants was measured using a UV-Vis spectrophotometer to calculate the degradation rate.

[0009] The aforementioned porous carbon catalyst for microwave pyrolysis of waste plastics and its application in the degradation of organic pollutants by activated PMS are characterized by: a simple catalyst preparation process, short preparation time, and the optimal catalyst exhibiting obvious porous morphological structure characteristics; compared with traditional pyrolysis methods, microwave treatment and the introduction of PC successfully induced the co-carbonization of difficult-to-carbonize plastics (PP / PES), with the introduction of PP significantly improving the graphitization degree and specific surface area of ​​the material (reaching 934.99 m²). 2 / g) and defect vacancy concentration, while the introduction of PES successfully achieved in-situ doping of thiophene S and C=O functional groups.

[0010] The application of the porous carbon material catalyst prepared by microwave carbonization of waste plastics in the degradation of organic pollutants is characterized by the high degradation efficiency of the prepared porous carbon material catalysts PC1PP3 and PC1PES3 for organic pollutants. At a high PMS concentration (0.7 g / L), the degradation rate constant for sulfamethoxazole reaches 0.261 min. -1 and 0.256min -1In particular, the PC1PP3 catalyst still exhibits excellent performance at a low PMS dosage (0.3 g / L), achieving a 100% removal rate of sulfamethoxazole and a PMS utilization efficiency (PUE) as high as 92.5%, which is significantly better than conventional carbon materials. In addition, this system has good broad-spectrum degradation capabilities for sulfamethoxazole, 5-aminotetrazole, benzyl chloroformate, tetracycline, oxytetracycline, bisphenol A, p-chlorophenol, and p-nitrophenol.

[0011] The application of the porous carbon material catalyst prepared by microwave carbonization of waste plastics in the degradation of organic pollutants is characterized by: achieving directional switching of the catalytic mechanism by controlling the composition of the waste plastics. In the PC1PP3 / PMS catalytic system, the highly graphitized structure and abundant defect sites construct a high-speed electron transport channel, dominating the non-radical direct electron transfer pathway for pollutant degradation; in the PC1PES3 / PMS catalytic system, the thiophene sulfur-modified C=O sites promote singlet oxygen (… 1 The generation of O2 dominates the degradation of pollutants via the non-radical singlet oxygen pathway; both systems exhibit excellent resistance to background ion interference. Instruction manual illustrations

[0012] Figure 1 (a) is a schematic diagram of the synthesis of PC1PP3 and PC1PES3. Figure 1 (b) is the SEM image of PC1PP3. Figure 1 (c) is a TEM image of PC1PP3. Figure 1 (d) is the SEM image of PC1PES3. Figure 1 (e) is a TEM image of PC1PES3.

[0013] Figure 2 (a) is PC x PP y X-ray diffraction (XRD) pattern compared with control sample C; Figure 2 (b) is PC x PES y XRD patterns of control sample C.

[0014] Figure 3 The attached diagram shows the nitrogen adsorption and desorption of PC1PP3, PC1PES3, and control sample C.

[0015] Figure 4 (a) XPS full spectrum scans of PC1PP3, PC1PES3 catalysts and control sample C; Figure 4 (b) High-resolution XPS images of PC1PP3, PC1PES3 and control sample C at C1s; Figure 4(c) High-resolution XPS images of PC1PP3, PC1PES3 and control sample C at 0 1s; Figure 4 (d) is the S 2p high-resolution XPS image of the PC1PES3 catalyst. Detailed Implementation

[0016] The present invention will be described in detail below with reference to specific implementation examples.

[0017] Implementation Case 1: The specific preparation steps for porous carbon material catalysts are as follows: 1.5g of thoroughly ground plastic powder was mixed with 0.5g of sodium hydroxide and placed in a 25mL crucible. The mixture was then pyrolyzed at 800W microwave power for 2 minutes to obtain porous carbon precursor PC. x PP y or PC x PES y Where x:y represents the mass ratio of PC to PP and PC to PES, with values ​​of 2:1, 1:1, 1:2, 1:3, and 1:4, respectively; the precursor is then repeatedly washed with deionized water until the pH of the washing solution is neutral, and then vacuum dried at 60°C for 12 hours to obtain the final porous carbon catalyst material. Figure 1 a) It is worth noting that under the same preparation conditions, microwaves can directly carbonize PC powder in the presence of sodium hydroxide, but it is difficult to carbonize PP or PES powder. Therefore, in the carbonization process of mixed plastics, the carbon material formed by microwave carbonization of PC in the presence of sodium hydroxide can further promote the microwave carbonization of PP / PES. In summary, PC can serve as an effective auxiliary agent for the carbonization of PP and PES, while sodium hydroxide can act as both a microwave absorber and a pore-forming agent in this process.

[0018] Figure 1 (a) is a schematic diagram of the synthesis of PC1PP3 and PC1PES3. Figure 1 (b) is the SEM image of PC1PP3. Figure 1 (c) is a TEM image of PC1PP3. Figure 1 (d) is the SEM image of PC1PES3. Figure 1(e) is a TEM image of PC1PES3. Characterization results from scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show that the non-metallic carbon catalysts exhibit different porous structures: PC-derived carbon exhibits an irregular blocky structure with a relatively small number of pores. PC1PP3 possesses a sponge-like porous structure with unique internal carbon vesicles. This should be attributed to the rapid release of large amounts of alkane volatiles from the flexible alkyl chains of PP during microwave pyrolysis, thereby forming channels within the carbon framework. Furthermore, the deep etching of the channel walls by sodium hydroxide produces micropores and mesopores. Simultaneously, the aromatic ring chains of PC inhibit the structural collapse caused by PP pyrolysis, ultimately leading to the formation of numerous irregular defect pores (…). Figure 1 b- Figure 1 c). When PP is replaced by PES, PC1PES3 exhibits abundant coral-like pores, with interlayer fiber bridges interwoven to form a three-dimensional interconnected network. Figure 1 d- Figure 1 e). The differences in the porous structures mentioned above should stem from the different chain structure mechanisms of PP and PES, ultimately reflecting the relationship between polymer chain structure, carbon material morphology, structure, and activity. In PP, flexible chains dominate channel connectivity, while in PES, rigid heteroatom chains dominate structural dispersion.

[0019] Figure 2 (a, b) show the characterization of the crystal structure of the prepared catalytic material using X-ray diffraction (XRD): the prepared carbon material (PC) x PP y and PC x PES y The series exhibits two broad and weak diffraction peaks near 23.8° and 44.1°, corresponding to the (002) crystal plane of amorphous carbon and the (100) crystal plane of graphitic carbon, respectively. This indicates that waste plastics have been successfully converted into carbon materials with typical amorphous structures after microwave-assisted pyrolysis. It is worth noting that in Figure 2 In (a), when the doping ratio of PP is too high (e.g., PC1PP4), sharp crystallization peaks appear in the spectrum, corresponding to the incomplete carbonization of polypropylene crystal structure. This result confirms that PC plays a key role in microwave absorption and induced carbonization in the mixed system. When the PC content is too low (less than 20%), it cannot provide enough heat energy to completely carbonize PP. Therefore, the optimal mass ratio of PC to regulator is determined to be 1:3 (i.e., PC1PP3). Figure 3The nitrogen adsorption-desorption isotherms and pore size distributions of each sample are shown. Comparative sample C exhibits a type IV isotherm, but with low adsorption capacity, indicating an underdeveloped pore structure. PC1PP3 shows extremely high nitrogen adsorption capacity, with a sharp increase in adsorption capacity in the low relative pressure region (P / P0 < 0.1), indicating abundant micropores; it also exhibits a significant hysteresis loop, indicating the presence of mesopores. Its specific surface area is calculated to be as high as 934.99 m². 2 / g, the pore volume increased significantly. This is because the flexible PP chains rapidly decompose and volatilize during microwave pyrolysis, "expanding" a large number of vesicle-like pores within the carbon skeleton. PC1PES3: Although the specific surface area (193.89 m²) 2 The concentration of 4g / g is lower than that of PC1PP3, but it is still significantly improved compared to pure PC carbon materials, exhibiting a hierarchical porous structure.

[0020] Figure 4 a) is an XPS full-spectrum scan, which confirmed that the material is mainly composed of C and O elements, and PC1PES3 also contains S element. Figure 4 b is the C 1s spectrum, where each sample shows peaks around 284.8 eV, 286.3 eV, 288.5 eV, and 290.2 eV, corresponding to CC / C=C, CO, OC=O, and π-π, respectively. * Key. PC1PP 3中 The high content of C=C bonds indicates a good degree of graphitization, which is beneficial for electrical conductivity. Figure 4 c is the O 1s spectrum, showing the presence of C=O, C-OH, and adsorbed oxygen. The high C=O content in PC1PES3 is consistent with its role in the singlet oxygen generation pathway. Figure 4 d is the S 2p spectrum (for PC1PES3 only). The characteristic peaks at 164.0 eV and 165.4 eV correspond to the spin orbital splitting (2p) of thiophene S (-CSC-). 3 / 2 and 2p 1 / 2 The peak at 168.1-169.3 eV corresponds to oxidized sulfur (C-SO₄). x -C). This confirms that sulfur in PES has been successfully doped in situ into the carbon framework, forming stable thiophene sulfur active sites.

[0021] The reaction conditions for the porous carbon catalyst to activate PMS to degrade organic pollutants are as follows: a porous carbon catalyst and PMS are added to a certain volume of water containing organic pollutants, wherein the amount of porous carbon catalyst added is 0.10-0.18 g / L, the initial concentration of PMS is 0.3-0.7 g / L, the reaction pH range is 3-11, and the reaction temperature range is 15-35℃.

[0022] Implementation Case 2 (See Table 1, Item 1, Degradation of SMX by C) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L of C catalyst and 0.7 g / L of PMS to a 100 mL round-bottom flask containing 50 mL of SMX (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). The degradation rate of SMX by C was found to be 38.3% within 25 minutes, with a rate constant of 0.0364 min. -1 .

[0023] Implementation Case 3 (See Table 1, Item 2, Degradation of SMX by PC2PP1) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC2PP1 catalyst and 0.7 g / L PMS to a 100 mL round-bottom flask containing 50 mL of SMX (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). The degradation rate of SMX by PC2PP1 was found to be 41.9% within 25 minutes, with a rate constant of 0.0494 min. -1 .

[0024] Implementation Case 4 (See Table 1, Item 3, Degradation of SMX by PC1PP1) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PP1 catalyst and 0.7 g / L PMS to a 100 mL round-bottom flask containing 50 mL of SMX (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). The degradation rate of SMX by PC1PP1 was found to be 56.1% within 25 minutes, with a rate constant of 0.0818 min. -1 .

[0025] Implementation Case 5 (See Table 1, Item 4, Degradation of SMX by PC1PP2) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PP2 catalyst and 0.7 g / L PMS to a 100 mL round-bottom flask containing 50 mL of SMX (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). The degradation rate of SMX by PC1PP2 was found to be 74.5% within 25 minutes, with a rate constant of 0.1220 min. -1 .

[0026] Implementation Case 6 (See Table 1, Item 5, Degradation of SMX by PC1PP3) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PP3 catalyst and 0.7 g / L PMS to a 100 mL round-bottom flask containing 50 mL of SMX (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). It was found that the degradation rate of SMX by PC1PP3 was 100% within 25 minutes, with a rate constant of 0.2539 min. -1 .

[0027] Implementation Case 7 (See Table 1, Item 6, Degradation of SMX by PC1PP4) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PP4 catalyst and 0.7 g / L PMS to a 100 mL round-bottom flask containing 50 mL of SMX (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). The degradation rate of SMX by PC1PP4 was found to be 85.1% within 25 minutes, with a rate constant of 0.1593 min⁻¹. -1 .

[0028] Implementation Case 8 (See Table 1, Item 7, Degradation of SMX by PC2PES1) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC2PES1 catalyst and 0.7 g / L PMS to a 100 mL round-bottom flask containing 50 mL of SMX (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). The degradation rate of SMX by PC2PES1 was found to be 54.9% within 25 minutes, with a rate constant of 0.0650 min. -1 .

[0029] Implementation Case 9 (See Table 1, Item 8, Degradation of SMX by PC1PES1) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PES1 catalyst and 0.7 g / L PMS to a 100 mL round-bottom flask containing 50 mL of SMX (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). The degradation rate of SMX by PC1PES1 was found to be 66.6% within 25 minutes, with a rate constant of 0.1014 min⁻¹. -1 .

[0030] Implementation Case 10 (See Table 1, Item 9, Degradation of SMX by PC1PES2) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PES2 catalyst and 0.7 g / L PMS to a 100 mL round-bottom flask containing 50 mL of SMX (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). The degradation rate of SMX by PC1PES2 was found to be 75.7% within 25 minutes, with a rate constant of 0.1401 min⁻¹. -1 .

[0031] Implementation Case 11 (See Table 1, Item 10, Degradation of SMX by PC1PES3) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PES3 catalyst and 0.7 g / L PMS to a 100 mL round-bottom flask containing 50 mL of SMX (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). It was found that the degradation rate of SMX by PC1PES3 was 100% within 25 minutes, with a rate constant of 0.2456 min. -1 .

[0032] Implementation Case 12 (See Table 1, Item 11, Degradation of SMX by PC1PES4) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PES4 catalyst and 0.7 g / L PMS to a 100 mL round-bottom flask containing 50 mL of SMX (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). The degradation rate of SMX by PC1PES4 was found to be 94.1% within 25 minutes, with a rate constant of 0.2245 min. -1 .

[0033]

[0034] Implementation Case 13 (See Table 2, Item 1, Degradation of SMX by C under 0.3 g / L PMS conditions) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L of C catalyst and 0.3 g / L of PMS to a 100 mL round-bottom flask containing 50 mL of SMX (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). The degradation rate of SMX by C was found to be 27.5% within 25 minutes, with a rate constant of 0.0274 min.-1 .

[0035] Implementation Case 14 (See Table 2, Item 2, Degradation of SMX by PC1PP3 under 0.3 g / L PMS conditions) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PP3 catalyst and 0.3 g / L PMS to a 100 mL round-bottom flask containing 50 mL of SMX (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). It was found that the degradation rate of SMX by PC1PP3 was 100% within 25 minutes, with a rate constant of 0.2322 min. -1 .

[0036] Implementation Case 15 (See Table 2, Item 3, Degradation of SMX by PC1PES3 under 0.3 g / L PMS conditions) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PES3 catalyst and 0.3 g / L PMS to a 100 mL round-bottom flask containing 50 mL of SMX (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). The degradation rate of SMX by PC1PES3 was found to be 74.5% within 25 minutes, with a rate constant of 0.0935 min. -1 .

[0037]

[0038] Implementation Case 16 (See Table 3, Item 1, Degradation of SMX by 0.10 g / L PC1PP3 for the reaction) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.10 g / L PC1PP3 catalyst and 0.3 g / L PMS to a 100 mL round-bottom flask containing 50 mL of SMX (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). The degradation rate of SMX by PC1PP3 was found to be 70.0% within 25 minutes.

[0039] Implementation Case 17 (See Table 3, Item 2, Degradation of SMX by 0.12 g / L PC1PP3 for the reaction) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.12 g / L PC1PP3 catalyst and 0.3 g / L PMS to a 100 mL round-bottom flask containing 50 mL of SMX (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). It was found that the degradation rate of SMX by PC1PP3 was 87.2% within 25 minutes.

[0040] Implementation Case 18 (See Table 3, Item 3, Degradation of SMX by 0.14 g / L PC1PP3 for the reaction) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.14 g / L PC1PP3 catalyst and 0.3 g / L PMS to a 100 mL round-bottom flask containing 50 mL of SMX (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). It was found that the degradation rate of SMX by PC1PP3 was 90.3% within 25 minutes.

[0041] Implementation Case 19 (See Table 3, Item 4, Degradation of SMX by 0.16 g / L PC1PP3 for the reaction) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PP3 catalyst and 0.3 g / L PMS to a 100 mL round-bottom flask containing 50 mL of SMX (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). It was found that the degradation rate of SMX by PC1PP3 was 100% within 25 minutes.

[0042] Implementation Case 20 (See Table 3, Item 5, Degradation of SMX by 0.18 g / L PC1PP3 for the reaction) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.18 g / L PC1PP3 catalyst and 0.3 g / L PMS to a 100 mL round-bottom flask containing 50 mL of SMX (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). It was found that the degradation rate of SMX by PC1PP3 was 100% within 25 minutes.

[0043]

[0044] Implementation Case 21 (See Table 4, Item 1, Effect of 0.2 g / L PMS on SMX Degradation by PC1PP3) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PP3 catalyst and 0.2 g / L PMS to a 100 mL round-bottom flask containing 50 mL of SMX (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). The degradation rate of SMX by PC1PP3 was found to be 89.6% within 25 minutes.

[0045] Implementation Case 22 (See Table 4, Item 3, Effect of 0.4 g / L PMS on SMX Degradation by PC1PP3) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PP3 catalyst and 0.4 g / L PMS to a 100 mL round-bottom flask containing 50 mL of SMX (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). It was found that the degradation rate of SMX by PC1PP3 was 100% within 25 minutes.

[0046] Implementation Case 23 (See Table 4, Item 4, Effect of 0.5 g / L PMS on SMX Degradation by PC1PP3) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PP3 catalyst and 0.5 g / L PMS to a 100 mL round-bottom flask containing 50 mL of SMX (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). It was found that the degradation rate of SMX by PC1PP3 was 99.4% within 25 minutes.

[0047] Implementation Case 24 (See Table 4, Item 5, Effect of 0.6 g / L PMS on SMX Degradation by PC1PP3) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PP3 catalyst and 0.6 g / L PMS to a 100 mL round-bottom flask containing 50 mL of SMX (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). It was found that the degradation rate of SMX by PC1PP3 was 99.7% within 25 minutes.

[0048] Implementation Case 25 (See Table 4, Item 7, Effect of 0.8 g / L PMS on SMX Degradation by PC1PP3) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PP3 catalyst and 0.8 g / L PMS to a 100 mL round-bottom flask containing 50 mL of SMX (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). It was found that the degradation rate of SMX by PC1PP3 was 98.7% within 25 minutes.

[0049]

[0050] Implementation Case 26 (See Table 5, Item 1, Effect of 0.2 g / L PMS on SMX Degradation by PC1PES3) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PES3 catalyst and 0.2 g / L PMS to a 100 mL round-bottom flask containing 50 mL of SMX (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). It was found that the degradation rate of SMX by PC1PES3 was 70.7% within 25 minutes.

[0051] Implementation Case 27 (See Table 5, Item 3, Effect of 0.4 g / L PMS on SMX Degradation by PC1PES3) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PES3 catalyst and 0.4 g / L PMS to a 100 mL round-bottom flask containing 50 mL of SMX (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). The degradation rate of SMX by PC1PES3 was found to be 78.4% within 25 minutes.

[0052] Implementation Case 28 (See Table 5, Item 4, Effect of 0.5 g / L PMS on SMX Degradation by PC1PES3) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PES3 catalyst and 0.5 g / L PMS to a 100 mL round-bottom flask containing 50 mL of SMX (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). The degradation rate of SMX by PC1PES3 was found to be 81.1% within 25 minutes.

[0053] Implementation Case 29 (See Table 5, Item 5, Effect of 0.6 g / L PMS on SMX Degradation by PC1PES3) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PES3 catalyst and 0.6 g / L PMS to a 100 mL round-bottom flask containing 50 mL of SMX (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). The results showed that the degradation rate of SMX by PC1PES3 was 90.5% within 25 minutes.

[0054] Implementation Case 30 (See Table 5, Item 7, Effect of 0.8 g / L PMS on SMX Degradation by PC1PES3) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PES3 catalyst and 0.8 g / L PMS to a 100 mL round-bottom flask containing 50 mL of SMX (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). It was found that the degradation rate of SMX by PC1PES3 was 100% within 25 minutes.

[0055]

[0056] Implementation Case 31 (See Table 6, Item 1 for the reaction, PC1PP3 degradation of SMX at a concentration of 5 mg / L) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PP3 catalyst and 0.7 g / L PMS to a 100 mL round-bottom flask containing 50 mL of SMX (5 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). It was found that the degradation rate of SMX by PC1PP3 was 100% within 25 minutes.

[0057] Implementation Case 32 (See Table 6, Item 2, SMX degradation concentration of PC1PP3 at 8 mg / L) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PP3 catalyst and 0.7 g / L PMS to a 100 mL round-bottom flask containing 50 mL of SMX (8 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). It was found that the degradation rate of SMX by PC1PP3 was 100% within 25 minutes.

[0058] Implementation Case 33 (See Table 6, Item 4 for the reaction, SMX with PC1PP3 degradation concentration of 15 mg / L) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PP3 catalyst and 0.7 g / L PMS to a 100 mL round-bottom flask containing 50 mL of SMX (15 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). It was found that the degradation rate of SMX by PC1PP3 was 96.7% within 25 minutes.

[0059] Implementation Case 34 (See Table 6, Item 5 for the reaction, SMX with PC1PP3 degradation concentration of 20 mg / L) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PP3 catalyst and 0.7 g / L PMS to a 100 mL round-bottom flask containing 50 mL of SMX (20 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). It was found that the degradation rate of SMX by PC1PP3 was 87.3% within 25 minutes.

[0060]

[0061] Implementation Case 35 (See Table 7, Items 1-6 for responses) To evaluate the stability of the catalyst, six cycles were conducted. After each run, the resulting sample was collected by filtration, washing, and vacuum drying overnight, and the solid obtained was used for the next cycle. The temperature of the thermostatically stirred water bath was set at 25±2℃, and the initial pH was adjusted to 6.8 with 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PP3 catalyst and 0.7 g / L PMS to a 100 mL round-bottom flask containing 50 mL of SMX (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). It was found that the degradation rate of SMX by PC1PP3 was 100% within 25 minutes. This rate remained above 90% in the first four cycles, reached 86.7% in the fifth cycle, and 84.0% in the sixth cycle.

[0062]

[0063] Implementation Case 36 (See Table 8, Items 1-6 for responses) To evaluate the stability of the catalyst, six cycles were conducted. After each run, the resulting sample was collected by filtration, washing, and vacuum drying overnight, and the solid obtained was used for the next cycle. The temperature of the thermostatically stirred water bath was set at 25±2℃, and the initial pH was adjusted to 6.8 with 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PES3 catalyst and 0.7 g / L PMS to a 100 mL round-bottom flask containing 50 mL of SMX (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of sulfamethoxazole was determined using a UV-Vis spectrophotometer (267 nm). It was found that the degradation rate of SMX by PC1PES3 was 100% within 25 minutes. The success rate remained above 90% in the first two cycles, 87.2% in the third cycle, 82.2% in the fourth cycle, 80.0% in the fifth cycle, and 76.7% in the sixth cycle.

[0064]

[0065] Implementation Case 37 (See Table 9, Item 1, Degradation of 5-aminotetrazole (ATZ) by PC1PP3 catalyst) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PP3 catalyst and 0.7 g / L PMS to a 100 mL round-bottom flask containing 50 mL of ATZ (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of 5-aminotetrazolium was determined using a UV-Vis spectrophotometer (260 nm). The degradation rate of ATZ by PC1PP3 was found to be 99.3% within 25 minutes.

[0066] Implementation Case 38 (See Table 9, Item 2, Degradation of benzyl chloroformate (CBZ) by PC1PP3 catalyst) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PP3 catalyst and 0.7 g / L PMS to a 100 mL round-bottom flask containing 50 mL of CBZ (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of benzyl chloroformate was determined using a UV-Vis spectrophotometer (286 nm). It was found that the degradation rate of CBZ by PC1PP3 was 98.1% within 25 minutes.

[0067] Implementation Case 39 (See Table 9, Item 3, Degradation of Tetracycline (TC) by PC1PP3 Catalyst) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PP3 catalyst and 0.7 g / L PMS to a 100 mL round-bottom flask containing 50 mL of TC (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The tetracycline concentration was measured using a UV-Vis spectrophotometer (357 nm). It was found that the degradation rate of TC by PC1PP3 was 98.9% within 10 minutes.

[0068] Implementation Case 40 (See Table 9, Item 4, Degradation of Oxytetracycline (OTC) by PC1PP3 Catalyst) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PP3 catalyst and 0.7 g / L PMS to a 100 mL round-bottom flask containing 50 mL of OTC (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of oxytetracycline was determined using a UV-Vis spectrophotometer (358 nm). It was found that the degradation rate of OTC by PC1PP3 was 99.4% within 10 minutes.

[0069] Implementation Case 41 (See Table 9, Item 5, Degradation of Bisphenol A (BPA) by PC1PP3 Catalyst) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PP3 catalyst and 0.7 g / L PMS to a 100 mL round-bottom flask containing 50 mL of BPA (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of bisphenol A was measured using a UV-Vis spectrophotometer (276 nm). It was found that the degradation rate of BPA by PC1PP3 was 99.4% within 10 minutes.

[0070] Implementation Case 42 (See Table 9, Item 6, Degradation of p-chlorophenol (4-CP) by PC1PP3 catalyst) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PP3 catalyst and 0.7 g / L PMS to a 100 mL round-bottom flask containing 50 mL of 4-CP (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of p-chlorophenol was measured using a UV-Vis spectrophotometer (280 nm). The degradation rate of 4-CP by PC1PP3 was found to be 99.2% within 25 minutes.

[0071] Implementation Case 43 (See Table 9, Item 7, Degradation of p-nitrophenol (4-NP) by PC1PP3 catalyst) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PP3 catalyst and 0.7 g / L PMS to a 100 mL round-bottom flask containing 50 mL of 4-NP (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of p-nitrophenol was measured using a UV-Vis spectrophotometer (317 nm). The degradation rate of 4-NP by PC1PP3 was found to be 82.6% within 25 minutes.

[0072]

[0073] Implementation Case 44 (Reaction see Table 10, Item 1, Degradation of 5-aminotetrazole (ATZ) by PC1PES3 catalyst) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PES3 catalyst and 0.7 g / L PMS to a 100 mL round-bottom flask containing 50 mL of ATZ (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of 5-aminotetrazolium was determined using a UV-Vis spectrophotometer (260 nm). The degradation rate of ATZ by PC1PES3 was found to be 89.0% within 25 minutes.

[0074] Implementation Case 45 (Reaction see Table 10, Item 2, Degradation of benzyl chloroformate (CBZ) by PC1PES3 catalyst) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PES3 catalyst and 0.7 g / L PMS to a 100 mL round-bottom flask containing 50 mL of CBZ (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of benzyl chloroformate was determined using a UV-Vis spectrophotometer (286 nm). It was found that the degradation rate of CBZ by PC1PES3 was 86.5% within 25 minutes.

[0075] Implementation Case 46 (Reaction see Table 10, Item 3, Degradation of Tetracycline (TC) by PC1PES3 Catalyst) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PES3 catalyst and 0.7 g / L PMS to a 100 mL round-bottom flask containing 50 mL of TC (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The tetracycline concentration was measured using a UV-Vis spectrophotometer (357 nm). It was found that the degradation rate of TC by PC1PES3 was 98.3% within 10 minutes.

[0076] Implementation Case 47 (See Table 10, Item 4, Degradation of Oxytetracycline (OTC) by PC1PES3 Catalyst) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PES3 catalyst and 0.7 g / L PMS to a 100 mL round-bottom flask containing 50 mL of OTC (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of oxytetracycline was determined using a UV-Vis spectrophotometer (358 nm). It was found that the degradation rate of OTC by PC1PES3 was 98.7% within 10 minutes.

[0077] Implementation Case 48 (See Table 10, Item 5, Degradation of Bisphenol A (BPA) by PC1PES3 Catalyst) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PES3 catalyst and 0.7 g / L PMS to a 100 mL round-bottom flask containing 50 mL of BPA (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of bisphenol A was measured using a UV-Vis spectrophotometer (276 nm). It was found that the degradation rate of BPA by PC1PES3 was 99.5% within 20 minutes.

[0078] Implementation Case 49 (See Table 10, Item 6, Degradation of p-chlorophenol (4-CP) by PC1PES3 catalyst) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PES3 catalyst and 0.7 g / L PMS to a 100 mL round-bottom flask containing 50 mL of 4-CP (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of p-chlorophenol was measured using a UV-Vis spectrophotometer (280 nm). The degradation rate of 4-CP by PC1PES3 was found to be 49.8% within 25 minutes.

[0079] Implementation Case 50 (See Table 10, Item 7, Degradation of p-nitrophenol (4-NP) by PC1PES3 catalyst) The temperature of the thermostatically heated magnetically stirred water bath was set to 25±2℃, and the initial pH was adjusted to 6.8 using 0.1M HCl / NaOH. The degradation reaction was initiated by adding 0.16 g / L PC1PES3 catalyst and 0.7 g / L PMS to a 100 mL round-bottom flask containing 50 mL of 4-NP (10 mg / L) aqueous solution. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of p-nitrophenol was measured using a UV-Vis spectrophotometer (317 nm). The degradation rate of 4-NP by PC1PES3 was found to be 88.2% within 25 minutes.

[0080]

[0081] Implementation Case 51 (See Table 11 for the reaction; the effect of the C / PMS system on SMX degradation in the presence of the quencher) Methanol (MeOH) and tert-butanol (TBA) are commonly used as free radical quenchers. MeOH can quench SO42-. •- TBA can quench ·OH, while p-benzoquinone (BQ) and curcumin (Cur) can quench O2, respectively. •- and 1 O2, while potassium dichromate (K2Cr2O7) is usually used as an electron (e) − The temperature of the thermostatically stirred water bath was set to 25±2℃. The initial pH was adjusted to 6.8 with 0.1M HCl / NaOH. 0.16 g / L of C catalyst and 10 mmol / L of quencher were added to a 100 mL round-bottom flask containing 50 mL of sulfamethoxazole aqueous solution (10 mg / L). Then, 0.7 g / L of PMS was added to the reactor to initiate the degradation reaction. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into centrifuge tubes containing 1 mL of methanol. The concentration of SMX in the solution was then detected at 267 nm using a UV-Vis spectrophotometer. It was found that under the quenching effects of MeOH, TBA, BQ, Cur, and K2Cr2O7, the degradation rates of SMX by C catalyst within 25 minutes were 36.8%, 35.7%, 34.9%, 14.4%, and 34.8%, respectively. Quenching results showed that the degradation rate of SMX decreased significantly after the addition of Cur, indicating that... 1 O2 plays a crucial role in the degradation process. In contrast, the degradation rate did not change significantly after the addition of MeOH, TBA, BQ, and K2Cr2O7, indicating that SO42- •- ·OH, O2 •-The contribution of electron transfer pathways to SMX removal in the C / PMS system is very limited. In general, the degradation of SMX in the C / PMS system is mainly driven by non-radical components. 1 The O2 pathway is dominant.

[0082]

[0083] Implementation Case 52 (Reactions are shown in Table 12, the effect of the PC1PP3 / PMS system on SMX degradation in the presence of quencher) Methanol (MeOH) and tert-butanol (TBA) are commonly used as free radical quenchers. MeOH can quench SO42-. •- TBA can quench ·OH, while p-benzoquinone (BQ) and curcumin (Cur) can quench O2, respectively. •- and 1 O2, while potassium dichromate (K2Cr2O7) is usually used as an electron (e) - The temperature of the thermostatically stirred water bath was set to 25±2℃. The initial pH was adjusted to 6.8 with 0.1M HCl / NaOH. 0.16 g / L of PC1PP3 catalyst and 10 mmol / L of quencher were added to a 100 mL round-bottom flask containing 50 mL of sulfamethoxazole aqueous solution (10 mg / L). Then, 0.7 g / L of PMS was added to the reactor to initiate the degradation reaction. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of SMX in the solution was then detected at 267 nm using a UV-Vis spectrophotometer. It was found that under the quenching effects of MeOH, TBA, BQ, Cur, and K2Cr2O7, the degradation rates of SMX by the PC1PP3 catalyst within 25 minutes were 97.3%, 92.2%, 88.8%, 85.0%, and 15.2%, respectively. Quenching results showed that the degradation rate of SMX was not significantly inhibited after the addition of MeOH, TBA, BQ, and Cur, indicating that free radicals (SO4) were not significantly inhibited. •- ·OH, O2 •- ) and singlet oxygen ( 1 O2 does not play a dominant role in the PC1PP3 / PMS system. However, the degradation rate of SMX decreased sharply after the addition of electron trapping agent K2Cr2O7, which confirms that electron transfer is the main pathway for PC1PP3 to activate PMS to degrade pollutants. This is attributed to the highly graphitized structure and abundant defect sites in the PC1PP3 material, which create efficient electron transport channels.

[0084]

[0085] Implementation Case 53 (Reactions are shown in Table 13, the effect of the PC1PES3 / PMS system on SMX degradation in the presence of quencher) Methanol (MeOH) and tert-butanol (TBA) are commonly used as free radical quenchers. MeOH can quench SO42-. •- TBA can quench ·OH, while p-benzoquinone (BQ) and curcumin (Cur) can quench O2, respectively. •- and 1 O2, while potassium dichromate (K2Cr2O7) is usually used as an electron (e) - The temperature of the thermostatically stirred water bath was set to 25±2℃. The initial pH was adjusted to 6.8 with 0.1M HCl / NaOH. 0.16 g / L of PC1PES3 catalyst and 10 mmol / L of quencher were added to a 100 mL round-bottom flask containing 50 mL of sulfamethoxazole aqueous solution (10 mg / L). Then, 0.7 g / L of PMS was added to the reactor to initiate the degradation reaction. At predetermined time intervals, 1.5 mL of the reaction solution was extracted, filtered through a 0.22 µm microporous membrane, and squeezed into a centrifuge tube containing 1 mL of methanol. The concentration of SMX in the solution was then detected at 267 nm using a UV-Vis spectrophotometer. It was found that under the quenching effects of MeOH, TBA, BQ, Cur, and K2Cr2O7, the degradation rates of SMX by the PC1PES3 catalyst within 25 minutes were 97.6%, 98.1%, 90.1%, 23.4%, and 77.9%, respectively. Quenching results showed that even after the addition of MeOH, TBA, and BQ, the degradation rate of SMX remained above 90%, indicating that free radicals (SO4) were effectively neutralized. •- ·OH, O2 •- Its contribution to this system is negligible. The degradation rate decreased slightly after the addition of K₂Cr₂O₇, indicating that the electron transfer pathway played a certain auxiliary role. However, after the addition of Cur, the degradation rate of SMX plummeted (to only 23.4%), which strongly suggests that non-radical singlet oxygen (…) contributes very little to the degradation. 1 O2 is the dominant active species in the PC1PES3 / PMS system for degrading pollutants, which is related to the thiophene sulfur doping modification of the C=O sites in PC1PES3, thereby promoting... 1 This is consistent with the mechanism of O2 generation.

[0086]

Claims

1. The application of microwave pyrolysis porous carbon catalyst for waste plastics and its activated PMS for degrading organic pollutants, characterized in that: Using polycarbonate (PC) waste plastic as the basic carbon source, polypropylene (PP) or polyethersulfone (PES) waste plastic was added respectively, and sodium hydroxide was used as a microwave absorber and pore-forming agent. A porous carbon catalyst with tunable active sites was rapidly prepared in one step by microwave-assisted one-pot solid-phase pyrolysis. The porous carbon catalyst exhibited excellent organic pollutant degradation performance in the PMS activation system. The specific steps for preparing the porous carbon catalyst are as follows: 1.5g of a plastic powder mixture, thoroughly ground into a uniform powder, is mixed with 0.5g of sodium hydroxide and placed in a 25mL crucible. The mixture is then pyrolyzed at 800W microwave power for 2 minutes to obtain the porous carbon precursor PC. x PP y or PC x PES y Where x:y represents the mass ratio of PC to PP and PC to PES, with values ​​of 2:1, 1:1, 1:2, 1:3, and 1:4, respectively; then the precursor is repeatedly washed with deionized water until the pH of the washing solution is neutral, and then vacuum dried at 60°C for 12 hours to obtain the final porous carbon catalyst material. The reaction conditions for the porous carbon catalyst to activate PMS to degrade organic pollutants are as follows: a porous carbon catalyst and PMS are added to a certain volume of water containing organic pollutants, wherein the amount of porous carbon catalyst added is 0.10-0.18 g / L, the initial concentration of PMS is 0.3-0.7 g / L, the reaction pH range is 3-11, and the reaction temperature range is 15-35℃.

2. The application of the porous carbon catalyst for microwave pyrolysis of waste plastics and its activated PMS for degrading organic pollutants according to claim 1, characterized in that: By adjusting the component ratio of waste plastics, the directional switching of catalytic degradation mechanisms can be achieved. When using PC1PP3 catalyst, it constructs direct electron transfer channels through its highly graphitized structure and defect vacancies, degrading organic pollutants primarily via a non-radical pathway. When using PC1PES3 catalyst, it promotes singlet oxygen degradation by introducing thiophene sulfur to modify the surface electronic structure of C=O sites. 1 O2 generation is primarily driven by the degradation of organic pollutants via the non-radical singlet oxygen pathway.

3. The application of the porous carbon catalyst for microwave pyrolysis of waste plastics and its activated PMS for degrading organic pollutants according to claim 1, characterized in that: The organic pollutants include sulfamethoxazole, 5-aminotetrazole, benzyl chloroformate, tetracycline, oxytetracycline, bisphenol A, p-chlorophenol, and p-nitrophenol; when sulfamethoxazole (SMX) is degraded, the degradation rate constant k of SMX in the PC1PP3 / PMS system is... obs It is 0.261 min -1 ; The degradation rate constant k of SMX in the PC1PES3 / PMS system obs It is 0.256 min -1 .

4. The application of the porous carbon catalyst for microwave pyrolysis of waste plastics and its activated PMS for degrading organic pollutants according to claim 1, characterized in that: The PC1PP3 catalyst exhibits extremely high oxidant utilization efficiency under PMS concentrations of 0.2–0.8 g / L; when degrading sulfamethoxazole at an initial concentration of 10 mg / L, the PC1PP3 / PMS system can achieve a PMS utilization rate of 92.5%.

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