Application of microwave-assisted biomass waste glycerin derived carbon aerogel material in organic pollutant degradation

Abstract

According to the method disclosed by the invention, the carbonization of the waste glycerol in the biodiesel production process under the alkaline condition is realized for the first time, and the prepared carbon aerogel catalytic material is used for efficiently activating peroxymonosulfate (PMS) to degrade organic pollutants such as oxytetracycline hydrochloride (OTC). Glycerol and Co (NO3) 2.6 H2O are mixed to form a cobalt metal glycerol complex (Co-MGC) precursor, and then the carbon aerogel catalyst Co-MGC-w is formed through simple microwave pyrolysis. The formation of Co-Ox sites, the introduction of oxygen vacancies and the increase of the specific surface area are beneficial to the improvement of the performance of the catalyst. The optimal catalyst Co-MGC-w realizes 99.0% of OTC removal rate within 6 minutes, and the rate is as high as 0.651 min <-1 >. Compared with a traditional pyrolysis mode, microwave treatment not only is more beneficial to formation and exposure of active sites (Co-Ox, oxygen vacancies and C = O groups) in a catalytic material, but also is beneficial to PMS catalytic activation. In addition, in the application of degradation of other pollutants, the Co-MGC-w / PMS system also shows good universality.

Description

Technical Field

[0001] The present invention relates to an application of microwave-assisted biomass waste glycerol-derived carbon aerogel material in the degradation of organic pollutants Background Art

[0002] Antibiotics have long been a focus of attention in numerous pharmaceuticals and personal care products because microbial communities can develop resistance to them. Environmental residues of various antibiotics can lead to increased microbial resistance and promote the spread of antibiotic resistance genes (ARGs). ARGs can be transferred from the environment to humans via bacterial hosts, negatively impacting human health and causing significant ecological damage. Oxytetracycline hydrochloride (OTC) is one of many widely used antibiotics. The polycyclic aromatic compounds in OTC are difficult to degrade naturally in the environment due to their extremely stable molecular structure. Furthermore, OTC residues in the environment may accumulate in the food chain, affecting human health and causing irreversible damage to the body, including joint diseases, endocrine disorders, kidney disease, and cancer. Therefore, there is an urgent need to develop efficient, economical, and environmentally friendly strategies to degrade OTC and mitigate the associated environmental risks.

[0003] Advanced oxidation processes (AOPs) have received more attention than other methods for removing antibiotics due to their fast reaction rates and high oxidation capacity. The persulfate activation system of AOPs generates a variety of free radical and non-radical active species by catalytically activating peroxymonosulfate (PMS) or peroxydisulfate (PDS). Compared with PDS, the asymmetric structure of PMS makes it easier to activate. In particular, it exhibits higher activation efficiency under the action of transition metal catalysts. In addition, transition metal-based catalysts (such as Co, Cu, Mn, Fe and their oxides) have become the preferred choice in pollutant degradation systems through PMS activation due to their comprehensive advantages such as excellent catalytic activity, ease of operation and mild reaction conditions. Cobalt-based materials are effective activators for PMS, Co 2+ and Co 3+ The cyclic mechanism between the catalyst and the catalyst can continuously activate PMS to generate free radical species, thereby effectively degrading organic pollutants. The abundant oxygen vacancies (OV), the increase in specific surface area (SSA), and the construction of a porous structure in the catalyst can significantly promote the activation of PMS and enable the rapid removal of pollutants. Summary of the Invention

[0004] This invention uses low-cost glycerol as the carbon source, transition metal salts as the active ingredient of the catalytic material, and KOH to promote the coordination between glycerol and the transition metal. After thorough mixing of all reagents in a crucible, simple microwave-assisted pyrolysis is performed for 3 minutes to prepare the carbon aerogel catalytic material. The catalyst preparation method of this invention is simple and time-efficient. The resulting carbon aerogel has extremely high porosity, effectively activates PMS to degrade organic pollutants, and is easily recyclable.

[0005] The present invention discloses an application of microwave-assisted biomass waste glycerol-derived carbon aerogel material in the degradation of organic pollutants. The invention is characterized in that: low-cost biomass waste glycerol is used as a carbon source, Co (NO3)2·6 H2O is used as an active component of the catalytic material, KOH is used to promote the coordination between glycerol and transition metals, and glycerol is carbonized into a three-dimensional porous carbon aerogel catalytic material through a simple and rapid microwave pyrolysis method. In addition, rich Co-O x species and oxygen vacancies.

[0006] The preparation steps of the above-mentioned carbon aerogel catalyst are as follows: 1.5 mL of glycerol, 2 mmol Co (NO3) 2•6H2O and 0.50 g of KOH are placed in a 100 mL crucible and stirred thoroughly; then the crucible is placed in a microwave oven at 300 W for 3 minutes, cooled to room temperature, rinsed with water / ethanol several times and dried in a vacuum drying oven at 60°C for 12 hours to obtain the carbon aerogel catalyst Co-MGC-w; for comparison, the above-mentioned glycerol, Co (NO3) 2•6H2O and KOH are mixed and placed in a tubular furnace and carbonized at 500°C in an Ar atmosphere for 2 hours. The catalyst is named Co-MGC-500; in addition, when other reaction conditions remain unchanged, only Co (NO3) 2•6H2O is replaced by Ni (NO3) 2•6H2O or Cu When (NO3)2•3H2O was substituted, the carbonized catalysts were named Ni-MGC-w and Cu-MGC-w; when KOH was replaced by KHCO3, K2CO3 and NaOH, the carbonized catalysts were named Co-MGC-w1, Co-MGC-w2 and Co-MGC-w3; Catalyst-activated peroxymonosulfate (PMS) degradation of organic pollutants: The degradation process was initiated by adding catalyst (0.1 g / L) and PMS (0.2 g / L) to a 50 mL aqueous solution containing 20 mg / L of organic pollutants at room temperature, adjusting the initial pH with 0.1 M sulfuric acid or sodium hydroxide. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was injected into a centrifuge tube prefilled with 1 mL of methanol, and the concentration of the organic pollutant was measured using a UV-visible spectrophotometer.

[0007] The above-mentioned microwave-assisted application of biomass waste glycerol-derived carbon aerogel material in the degradation of organic pollutants is characterized by: the catalyst preparation process is simple, the preparation time is short, the optimal catalyst exhibits a significant three-dimensional porous network structure, thus not only providing good adsorption capacity, but also providing a larger carrier surface for metal oxides; at the same time, the carbon aerogel catalytic material exhibits abundant oxygen vacancies and C=O groups, thereby facilitating the provision of more active sites; compared with traditional pyrolysis methods, microwave treatment is not only beneficial to the Co-O x The formation of carbon species and oxygen vacancies and the expansion of specific surface area are also beneficial to the generation of C=O in carbon materials.

[0008] The above-mentioned microwave-assisted biomass waste glycerol-derived carbon aerogel material is used in the degradation of organic pollutants. The characteristics of the above-mentioned material are that the prepared Co-MGC-w catalytic material has a high degradation efficiency for organic pollutants, and the removal rate of oxytetracycline (OTC) can reach 99.0% within 6 minutes, with a rate constant of up to 0.651 min −1 The removal rates for ciprofloxacin (CIP), carbamazepine (CBZ), norfloxacin (NOR), sulfamethoxazole (SMX), methyl red (MR), methylene blue (MB), methyl orange (MO), and rhodamine B (RhB) all reached 99.0%, 99.8%, 93.6%, 95.0%, 89.8%, 99.3%, 99.0%, and 99.6%, respectively. This demonstrates the excellent applicability of the Co-MGC-w / PMS system for different organic pollutants.

[0009] The above-mentioned microwave-assisted application of biomass waste glycerol-derived carbon aerogel material in the degradation of organic pollutants is characterized by: the microwave reaction successfully realizes the rapid carbonization of biomass waste glycerol, and the generated carbon aerogel material has a three-dimensional porous structure, which can provide more adsorption capacity in the pollutant degradation reaction. At the same time, the metal oxide can be evenly dispersed on the carrier surface, and the carbon aerogel catalytic material shows abundant oxygen vacancies and C=O groups, which is conducive to providing more active sites. In addition, in the Co-MGC-w / PMS catalytic system, the degradation of OTC is a non-radical pathway dominated by direct electron transfer, and PMS is catalytically activated to generate singlet oxygen. 1 O2 is the secondary active species.

[0010] Figures in the specification Figure 1 (a) and (b) are scanning electron microscope (SEM) images of Co-MGC-w; Figure 1 (c) Transmission electron microscopy (TEM) image of Co-MGC-w. Figure 1(d) High-resolution transmission electron microscopy (HRTEM) image of Co-MGC-w.

[0011] Figure 2 UV-visible spectra of Co(NO3)2·6H2O, glycerol + Co(NO3)2·6H2O and Co-MGC.

[0012] Figure 3 (a) and (b) are X-ray diffraction (XRD) patterns of the catalyst precursor Co-MGC and the catalysts Co-MGC-w, Cu-MGC-w, Ni-MGC-w, Co-MGC-w1, Co-MGC-w2, Co-MGC-w3, and CoO; Figure 3 (c) is the Raman spectra of Co-MGC-w and Co-MGC-500; Figure 3 (d) is the comparison of Raman spectra of Co-MGC-w and CoO; Figure 3 (e) Nitrogen adsorption / desorption isotherms of Co-MGC-w and Co-MGC-500 (inset: pore size distribution).

[0013] Figure 4 (a) Full X-ray photoelectron spectroscopy (XPS) spectrum of the Co-MGC-w catalyst. Detailed XPS spectra: (b) Co 2p, (c) O 1s, and (d) C 1s. DETAILED DESCRIPTION

[0014] The present invention is described in detail below with reference to specific implementation cases.

[0015] Implementation Case 1: The specific preparation steps of carbon aerogel catalyst are: 1.5 mL of glycerol, 0.58 g of Co(NO3)2·6H2O (2 mmol) and 0.50 g of KOH were placed in a 100 mL crucible and stirred thoroughly to obtain a glycerol metal complex (Co-MGC). The crucible was then placed in a microwave oven at 300 W for 3 minutes; after cooling to room temperature, it was washed with water / ethanol several times and dried in vacuum (60 ° C) for 12 hours to obtain the carbon aerogel catalyst Co-MGC-w; for comparison, the above-mentioned glycerol, Co (NO3) 2·6H2O and KOH mixture was placed in a tubular furnace and carbonized under Ar atmosphere (500 ° C, 2 hours), and the catalyst was named Co-MGC-500; when cobalt (II) nitrate hexahydrate was replaced by nickel (II) nitrate hexahydrate or copper nitrate trihydrate, the catalysts were named Ni-MGC-w and Cu-MGC-w; when KOH was replaced by KHCO3, K2CO3 and NaOH, the catalysts were named Co-MGC-w1, Co-MGC-w2 and Co-MGC-w3.

[0016] Figure 1 The structure and morphology of Co-MGC-w were obtained by SEM and TEM analysis. Figure 1 In (a), the Co-MGC-w catalyst exhibits a three-dimensional carbon aerogel structure. Figure 1 (b) is a magnified view of the wall of the Co-MGC-w carbon aerogel catalyst, indicating that the catalytic material is a porous structure. TEM analysis shows that the Co-MGC-w catalyst exhibits a porous structure with cobalt metal nanoparticles evenly distributed on the carbon support; the average particle size of these particles is 22.5 nm ( Figure 1 (c)). In HRTEM, the lattice fringes of 0.207 nm and 0.246 nm correspond to the Co(200) and CoO(111) planes ( Figure 1 (d)).

[0017] Figure 2 The formation of Co-MGC was analyzed using UV-visible spectroscopy. Aqueous Co(NO3)2•6H2O solutions exhibited distinct characteristic peaks at 299 and 512 nm. When glycerol was introduced, no new peaks were observed, indicating no coordination reaction between glycerol and cobalt nitrate. In a thoroughly mixed solution of glycerol, Co(NO3)2•6H2O, and KOH, the characteristic peaks at 299 and 512 nm disappeared, while a series of new peaks were observed at 368 nm, 429 nm, 526 nm, 587 nm, and 638 nm. This indicates that in the presence of KOH, the coordination reaction between glycerol and Co(NO3)2•6H2O formed Co-MGC.

[0018] Figure 3(a) and (b) XRD characterization of the crystal structures of the prepared catalysts Co-MGC, Co-MGC-w, Cu-MGC-w, Ni-MGC-w, Co-MGC-w1, Co-MGC-w2, Co-MGC-w3, and CoO. The XRD spectrum of the Co-MGC precursor shows obvious peaks in the range of 15°-75°, indicating that a coordination bond is successfully formed between glycerol and Co(NO3)2·6H2O in the presence of KOH. In the XRD pattern of Co-MGC-w, the broad diffraction peak near 24.6° is the graphitic carbon (002) crystal plane, indicating that glycerol is successfully carbonized. The diffraction peaks at 36.4°, 42.6°, 61.4°, 73.5°, and 77.5° are the (111), (200), (220), (311), and (100) crystal planes of CoO, respectively (JCPDS No. 71-1178). In addition to CoO, the signals near 44.2°, 51.5°, and 75.8° are the (111), (200), and (220) crystal planes of metallic Co (JCPDS No. 15-0806). Compared with Co-MCC-w prepared by microwave treatment, the diffraction peaks of CoO and Co in the Co-MC-500 catalyst obtained by conventional pyrolysis are less prominent. This indicates that the glycerol-derived Co-MGC-w is more conducive to the exposure of CoO and Co active sites. In order to verify the applicability of metal salts and bases to assist the carbonization of glycerol, nickel nitrate and copper nitrate were also used as substitutes for cobalt nitrate to assist the carbonization of glycerol. In the XRD of the carbon material Ni-MGC-w prepared in the presence of nickel nitrate, 44.54°, 51.94°, and 76.43° correspond to the (111), (200), and (220) crystal planes of metallic Ni (JCPDS No. 04-0850); at the same time, 37.12°, 43.16°, 62.85°, 75.36°, and 79.38° belong to the (111), (200), (220), (311), and (222) crystal planes of NiO (JCPDS No. 47-1049). The diffraction peaks at 43.3°, 50.5°, and 74.1° of Cu-MCC-w prepared in the presence of copper nitrate correspond to the (111), (200), and (220) crystal planes of metallic Cu (JCPDS No. 04-0836), respectively; the diffraction peaks at 35.4°, 38.7°, 48.7°, 58.2°, 61.5°, 65.8°, and 66.2° correspond to the (002), (111), (202), (204), (113), (022), and (311) crystal planes of CuO (JCPDS No. 48-1548). In addition, the effects of various bases on the carbonization of glycerol were further studied. When K2CO3, KHCO3, or NaOH was used as an alkaline additive and cobalt nitrate was used as a metal source, glycerol could also be well carbonized. However, the XRD pattern showed that ( Figure 3b) When K2CO3, KHCO3 or NaOH is used, it is not conducive to the production of active species cobalt oxide and metallic cobalt in the catalytic material.

[0019] Figure 3 (c) is the Raman spectra of Co-MGC-w and Co-MGC-500. -1 ) and D (1347 cm -1 The existence of ) bands indicates the graphitized carbon and disordered defect carbon structures of the two samples. D / I G It reflects the defect level and graphitization degree of carbon materials. It is worth noting that compared with Co-MGC-500 (I D / I G : 0.91) compared to Co-MGC-w’s I D / I G The value (1.02) is higher, which indicates that Co-MGC-w prepared by microwave pyrolysis is more likely to form defective carbon structures. Figure 3 (d) is the Raman spectrum comparison of Co-MGC-w and CoO. -1 The Co-O vibration peak in CoO is observed at . 1g The mode peak broadens and red-shifts to 697 cm -1 This transition indicates the existence of a large number of oxygen vacancies in Co-MGC-w.

[0020] The specific surface area and pore characteristics of the Co-MGC-w and Co-MGC-500 catalysts were tested by BET nitrogen adsorption-desorption isotherms. Figure 3 e). The isotherm of the catalyst is consistent with the type IV isotherm. It shows the typical H3 type hysteresis loop characteristics. The specific surface area of Co-MGC-w (166.6 m 2 / g) is higher than Co-MGC-500 (158.6 m 2 / g), indicating that microwave pyrolysis is beneficial to increasing the specific surface area and producing porous carbon materials.

[0021] Figure 4 XPS is used to detect the surface elemental composition and chemical valence state of the catalytic material. The full spectrum of Co-MGC-w and Co-MGC-500 catalytic materials is as follows Figure 4 As shown in (a), a large number of characteristic peaks of Co, C and O were detected. Figure 4 (b) shows the Co 2p3 / 2 peaks at 779.6, 781.1, and 782.0 eV for Co-MGC-w and Co-MGC-500, corresponding to the Co 0, Co(II) and Co-O x Compared with Co-MGC-500, the Co 0 , Co(II) and Co-O x The content is higher, indicating that microwave treatment promotes the formation of active species. Figure 4 (c) is the C 1s spectrum of Co-MGC-w and Co-MGC-500 catalysts. The C 1s peaks near 288.1, 286.4, and 284.8 eV correspond to C=O, CO, and C=C. From the C 1s spectrum, it can be seen that the C=O content in Co-MGC-w is higher than that in Co-MGC-500, which indicates that microwave treatment is beneficial to the formation of C=O bonds in Co-MGC-w. In addition, C=O bonds accelerate the activation of PMS to produce 1 O2, thereby improving the degradation efficiency of pollutants to a certain extent. Figure 4 (d) is the O 1s spectrum. The 531.6, 530.7 and 530.3 eV in O 1s correspond to oxygen vacancies, Co-O x The O 1s spectrum shows that the microwave-treated Co-MGC-w catalyst has a significantly increased oxygen vacancy content compared to the Co-MGC-500 catalyst calcined in a conventional tube furnace. These oxygen vacancies can be considered electron donors in the catalytic system, and the optimal number of O vacancies significantly enhances the activation of PMS.

[0022] Implementation Case 2 (Reaction see Table 1, Item 1) The temperature of the constant temperature magnetic stirring water bath was set at 25°C, and the initial pH was adjusted to 6.6 with 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.2 g / L PMS to a 100 mL round-bottom flask containing 50 mL of OTC (20 mg / L) aqueous solution. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was injected into a centrifuge tube containing 1 mL of methanol. The concentration of OTC was measured using a UV-visible spectrophotometer (352 nm). It was found that the degradation rate of OTC by PMS was 5.9% within 6 minutes, with a rate constant of 0.005 min. -1 .

[0023] Implementation Case 3 (Reaction see Table 1, Item 2) 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 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was started by adding 0.10 g / L CoO catalyst and 0.2 g / L PMS to a 100 mL round-bottom flask containing 50 mL of OTC (20 mg / L) aqueous solution. 1 mL of the reaction solution was extracted at predetermined time intervals, filtered using a 0.22µm microporous membrane, and the filtrate was injected into a centrifuge tube containing 1 mL of methanol. The concentration of OTC was measured using a UV-visible spectrophotometer (352 nm). It was found that the degradation rate of OTC by CoO catalyst was 33.9% within 6 minutes, with a rate constant of 0.078 min. -1 .

[0024] Implementation Case 4 (Reaction see Table 1, entry 3) The temperature of the constant temperature magnetic stirring water bath was set at 25°C, and the initial pH was adjusted to 6.6 with 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.10 g / L Ni-MGC-w catalyst and 0.2 g / L PMS to a 100 mL round-bottom flask containing 50 mL of OTC (20 mg / L) aqueous solution. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was injected into a centrifuge tube containing 1 mL of methanol. The concentration of OTC was measured using a UV-visible spectrophotometer (352 nm). It was found that the degradation rate of OTC by Ni-MGC-w catalyst was 91.0% within 6 minutes, with a rate constant of 0.439 min. -1 .

[0025] Implementation Case 5 (Reaction see Table 1, entry 4) 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 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was started by adding 0.10 g / L Cu-MGC-w catalyst and 0.2 g / L PMS to a 100 mL round-bottom flask containing 50 mL of OTC (20 mg / L) aqueous solution. 1 mL of the reaction solution was extracted at predetermined time intervals, filtered through a 0.22 µm microporous membrane, and the filtrate was injected into a centrifuge tube containing 1 mL of methanol. The concentration of OTC was measured using a UV-visible spectrophotometer (352 nm). It was found that the degradation rate of OTC by Cu-MGC-w catalyst was 93% within 6 minutes, with a rate constant of 0.498 min. -1 .

[0026] Implementation Case 6 (Reaction see Table 1, entry 5) The temperature of the constant temperature magnetic stirring water bath was set at 25°C, and the initial pH was adjusted to 6.6 with 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was started by adding 0.10 g / L Co-MGC-w catalyst and 0.2 g / L PMS to a 100 mL round-bottom flask containing 50 mL of OTC (20 mg / L) aqueous solution. 1 mL of the reaction solution was extracted at predetermined time intervals, filtered through a 0.22 µm microporous membrane, and the filtrate was injected into a centrifuge tube containing 1 mL of methanol. The concentration of OTC was measured using a UV-visible spectrophotometer (352 nm). It was found that the degradation rate of OTC by Co-MGC-w catalyst was 99.0% within 6 minutes, with a rate constant of 0.651 min. -1 .

[0027] Implementation Case 7 (Reaction see Table 1, entry 6) The temperature of the constant temperature magnetic stirring water bath was set at 25°C, and the initial pH was adjusted to 6.6 with 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.10 g / L Co-MGC-500 catalyst and 0.2 g / L PMS to a 100 mL round-bottom flask containing 50 mL of OTC (20 mg / L) aqueous solution. 1 mL of the reaction solution was extracted at predetermined time intervals, filtered through a 0.22 µm microporous membrane, and the filtrate was injected into a centrifuge tube containing 1 mL of methanol. The concentration of OTC was measured using a UV-visible spectrophotometer (352 nm). It was found that the degradation rate of OTC by the Co-MGC-500 catalyst was 79.0% within 6 minutes, with a rate constant of 0.352 min. -1 .

[0028] Implementation Case 8 (Reaction see Table 1, entry 7) The temperature of the constant temperature magnetic stirring water bath was set at 25°C, and the initial pH was adjusted to 6.6 with 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.10 g / L Co-MGC-w1 catalyst and 0.2 g / L PMS to a 100 mL round-bottom flask containing 50 mL of OTC (20 mg / L) aqueous solution. 1 mL of the reaction solution was extracted at predetermined time intervals, filtered through a 0.22 µm microporous membrane, and the filtrate was injected into a centrifuge tube containing 1 mL of methanol. The concentration of OTC was measured using a UV-visible spectrophotometer (352 nm). It was found that the degradation rate of OTC by Co-MGC-w1 catalyst was 97.0% within 6 minutes, with a rate constant of 0.538 min. -1 .

[0029] Implementation Case 9 (Reaction see Table 1, entry 8) The temperature of the constant temperature magnetic stirring water bath was set at 25°C, and the initial pH was adjusted to 6.6 with 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.10 g / L Co-MGC-w2 catalyst and 0.2 g / L PMS to a 100 mL round-bottom flask containing 50 mL of OTC (20 mg / L) aqueous solution. 1 mL of the reaction solution was extracted at predetermined time intervals, filtered through a 0.22 µm microporous membrane, and the filtrate was injected into a centrifuge tube containing 1 mL of methanol. The concentration of OTC was measured using a UV-visible spectrophotometer (352 nm). It was found that the degradation rate of OTC by Co-MGC-w2 catalyst was 94.0% within 6 minutes, with a rate constant of 0.459 min. -1 .

[0030] Example 10 (for reaction, see Table 1, entry 9) The temperature of the constant temperature magnetic stirring water bath was set at 25°C, and the initial pH was adjusted to 6.6 with 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.10 g / L Co-MGC-w3 catalyst and 0.2 g / L PMS to a 100 mL round-bottom flask containing 50 mL of OTC (20 mg / L) aqueous solution. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was injected into a centrifuge tube containing 1 mL of methanol. The concentration of OTC was measured using a UV-visible spectrophotometer (352 nm). It was found that the degradation rate of OTC by Co-MGC-w3 catalyst was 76.0% within 6 minutes, with a rate constant of 0.334 min. -1 .

[0031]

[0032] Implementation Case 11 (Reaction see Table 2, Item 1) The temperature of a thermostatically stirred water bath was set at 25°C, and the initial pH was adjusted to 6.6 using 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.06 g / L Co-MGC-w catalyst and 0.2 g / L PMS to 50 mL of an aqueous solution of OTC (20 mg / L) in a 100 mL round-bottom flask. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then poured into a centrifuge tube containing 1 mL of methanol. The OTC concentration was measured using a UV-visible spectrophotometer (352 nm). The degradation rate of OTC over the Co-MGC-w catalyst was 80.0% within 6 minutes.

[0033] Implementation Case 12 (Reaction see Table 2, Item 2) The temperature of a thermostatically stirred water bath was set at 25°C, and the initial pH was adjusted to 6.6 using 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.08 g / L Co-MGC-w catalyst and 0.2 g / L PMS to 50 mL of an aqueous solution of 20 mg / L OTC in a 100 mL round-bottom flask. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then poured into a centrifuge tube containing 1 mL of methanol. The OTC concentration was measured using a UV-visible spectrophotometer (352 nm). The degradation rate of OTC over the Co-MGC-w catalyst was 87.0% within 6 minutes.

[0034] Implementation Case 13 (Reaction see Table 2, Item 3) The temperature of a thermostatically stirred water bath was set at 25°C, and the initial pH was adjusted to 6.6 using 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.1 g / L Co-MGC-w catalyst and 0.2 g / L PMS to 50 mL of an aqueous solution of OTC (20 mg / L) in a 100 mL round-bottom flask. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then poured into a centrifuge tube containing 1 mL of methanol. The OTC concentration was measured using a UV-visible spectrophotometer (352 nm). The degradation rate of OTC over the Co-MGC-w catalyst was 99.0% within 6 minutes.

[0035] Implementation Case 14 (Reaction see Table 2, entry 4) The temperature of a thermostatically stirred water bath was set at 25°C, and the initial pH was adjusted to 6.6 using 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.12 g / L Co-MGC-w catalyst and 0.2 g / L PMS to 50 mL of an aqueous solution of 20 mg / L OTC in a 100 mL round-bottom flask. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then poured into a centrifuge tube containing 1 mL of methanol. The OTC concentration was measured using a UV-visible spectrophotometer (352 nm). The degradation rate of OTC over the Co-MGC-w catalyst was 95.0% within 6 minutes.

[0036]

[0037] Implementation Case 15 (Reaction see Table 3, entry 1) The temperature of a thermostatically stirred water bath was set at 25°C, and the initial pH was adjusted to 6.6 using 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.1 g / L Co-MGC-w catalyst and 0.1 g / L PMS to 50 mL of an aqueous solution of 20 mg / L OTC in a 100 mL round-bottom flask. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then poured into a centrifuge tube containing 1 mL of methanol. The OTC concentration was measured using a UV-visible spectrophotometer (352 nm). The degradation rate of OTC over the Co-MGC-w catalyst was 80.5% within 6 minutes.

[0038] Implementation Case 16 (Reaction see Table 3, entry 2) The temperature of a thermostatically stirred water bath was set at 25°C, and the initial pH was adjusted to 6.6 using 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.1 g / L Co-MGC-w catalyst and 0.15 g / L PMS to 50 mL of an aqueous solution of OTC (20 mg / L) in a 100 mL round-bottom flask. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then poured into a centrifuge tube containing 1 mL of methanol. The OTC concentration was measured using a UV-visible spectrophotometer (352 nm). The degradation rate of OTC over the Co-MGC-w catalyst was 88.0% within 6 minutes.

[0039] Implementation Case 17 (Reaction see Table 3, entry 3) The temperature of a thermostatically stirred water bath was set at 25°C, and the initial pH was adjusted to 6.6 using 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.1 g / L Co-MGC-w catalyst and 0.2 g / L PMS to 50 mL of an aqueous solution of OTC (20 mg / L) in a 100 mL round-bottom flask. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then poured into a centrifuge tube containing 1 mL of methanol. The OTC concentration was measured using a UV-visible spectrophotometer (352 nm). The degradation rate of OTC over the Co-MGC-w catalyst was 99.0% within 6 minutes.

[0040] Implementation Case 18 (Reaction see Table 3, Item 4) The temperature of a thermostatically stirred water bath was set at 25°C, and the initial pH was adjusted to 6.6 using 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.1 g / L Co-MGC-w catalyst and 0.25 g / L PMS to 50 mL of an aqueous solution of 20 mg / L OTC in a 100 mL round-bottom flask. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then poured into a centrifuge tube containing 1 mL of methanol. The OTC concentration was measured using a UV-visible spectrophotometer (352 nm). The degradation rate of OTC over the Co-MGC-w catalyst was 98.0% within 6 minutes.

[0041]

[0042] Implementation Case 19 (Reaction see Table 4, Item 1) The temperature of a thermostatically stirred water bath was set at 25°C, and the initial pH was adjusted to 3.0 using 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.1 g / L Co-MGC-w catalyst and 0.2 g / L PMS to 50 mL of an aqueous solution of 20 mg / L OTC in a 100 mL round-bottom flask. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then poured into a centrifuge tube containing 1 mL of methanol. The OTC concentration was measured using a UV-visible spectrophotometer (352 nm). The degradation rate of OTC over the Co-MGC-w catalyst was 76.9% within 6 minutes.

[0043] Implementation Case 20 (Reaction see Table 4, entry 2) The temperature of a thermostatically stirred water bath was set at 25°C, and the initial pH was adjusted to 5.0 using 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.1 g / L Co-MGC-w catalyst and 0.2 g / L PMS to 50 mL of an aqueous solution of 20 mg / L OTC in a 100 mL round-bottom flask. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then poured into a centrifuge tube containing 1 mL of methanol. The OTC concentration was measured using a UV-visible spectrophotometer (352 nm). The degradation rate of OTC over the Co-MGC-w catalyst was 89.5% within 6 minutes.

[0044] Implementation Case 21 (Reaction see Table 4, entry 3) The temperature of a thermostatically stirred water bath was set at 25°C, and the initial pH was adjusted to 6.6 using 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.1 g / L Co-MGC-w catalyst and 0.2 g / L PMS to 50 mL of an aqueous solution of OTC (20 mg / L) in a 100 mL round-bottom flask. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then poured into a centrifuge tube containing 1 mL of methanol. The OTC concentration was measured using a UV-visible spectrophotometer (352 nm). The degradation rate of OTC over the Co-MGC-w catalyst was 99.0% within 6 minutes.

[0045] Implementation Case 22 (Reaction see Table 4, Item 4) The temperature of a thermostatically stirred water bath was set at 25°C, and the initial pH was adjusted to 8 using 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.1 g / L Co-MGC-w catalyst and 0.2 g / L PMS to 50 mL of an aqueous solution of OTC (20 mg / L) in a 100 mL round-bottom flask. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then poured into a centrifuge tube containing 1 mL of methanol. The OTC concentration was measured using a UV-visible spectrophotometer (352 nm). The degradation rate of OTC over the Co-MGC-w catalyst was 93.2% within 6 minutes.

[0046] Implementation Case 23 (Reaction see Table 4, Item 5) The temperature of a thermostatically stirred water bath was set at 25°C, and the initial pH was adjusted to 11 using 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.1 g / L Co-MGC-w catalyst and 0.2 g / L PMS to 50 mL of an aqueous solution of OTC (20 mg / L) in a 100 mL round-bottom flask. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then poured into a centrifuge tube containing 1 mL of methanol. The OTC concentration was measured using a UV-visible spectrophotometer (352 nm). The degradation rate of OTC over the Co-MGC-w catalyst was 79.4% within 6 minutes.

[0047]

[0048] Implementation Case 24 (Reaction see Table 5, entry 1) The temperature of a thermostatically stirred water bath was set at 15°C, and the initial pH was adjusted to 6.6 using 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.1 g / L Co-MGC-w catalyst and 0.2 g / L PMS to 50 mL of an aqueous solution of OTC (20 mg / L) in a 100 mL round-bottom flask. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then poured into a centrifuge tube containing 1 mL of methanol. The OTC concentration was measured using a UV-visible spectrophotometer (352 nm). The degradation rate of OTC over the Co-MGC-w catalyst was 87.0% within 6 minutes.

[0049] Implementation Case 25 (for reaction, see Table 5, entry 2) The temperature of a thermostatically stirred water bath was set at 20°C, and the initial pH was adjusted to 6.6 using 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.1 g / L Co-MGC-w catalyst and 0.2 g / L PMS to 50 mL of an aqueous solution of OTC (20 mg / L) in a 100 mL round-bottom flask. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then poured into a centrifuge tube containing 1 mL of methanol. The OTC concentration was measured using a UV-visible spectrophotometer (352 nm). The degradation rate of OTC over the Co-MGC-w catalyst was 90.0% within 6 minutes.

[0050] Implementation Case 26 (for reactions, see Table 5, entry 3) The temperature of a thermostatically stirred water bath was set at 25°C, and the initial pH was adjusted to 6.6 using 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.1 g / L Co-MGC-w catalyst and 0.2 g / L PMS to 50 mL of an aqueous solution of OTC (20 mg / L) in a 100 mL round-bottom flask. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then poured into a centrifuge tube containing 1 mL of methanol. The OTC concentration was measured using a UV-visible spectrophotometer (352 nm). The degradation rate of OTC over the Co-MGC-w catalyst was 99.0% within 6 minutes.

[0051] Implementation Case 27 (Reaction see Table 5, entry 4) The temperature of a thermostatically stirred water bath was set at 30°C, and the initial pH was adjusted to 6.6 using 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.1 g / L Co-MGC-w catalyst and 0.2 g / L PMS to 50 mL of an aqueous solution of OTC (20 mg / L) in a 100 mL round-bottom flask. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then poured into a centrifuge tube containing 1 mL of methanol. The OTC concentration was measured using a UV-visible spectrophotometer (352 nm). The degradation rate of OTC over the Co-MGC-w catalyst was 99.0% within 6 minutes.

[0052]

[0053] Implementation Case 28 (Reaction see Table 6, entry 1) The temperature of the constant temperature magnetic stirring water bath was set to 25℃, and the initial pH was adjusted to 6.6 with 0.1 mol / L sulfuric acid or sodium hydroxide solution. - The degradation reaction was initiated by adding 0.1 g / L of Co-MGC-w catalyst and 0.2 g / L of PMS to a 100 mL round-bottom flask containing a 10 mM aqueous solution. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then injected into a centrifuge tube containing 1 mL of methanol. The concentration of OTC was measured using a UV-visible spectrophotometer (352 nm). The degradation rate of OTC over the Co-MGC-w catalyst was 83.0% within 6 minutes.

[0054] Implementation Case 29 (Reaction see Table 6, entry 2) Set the temperature of the constant temperature magnetic stirring water bath to 25℃ and adjust the initial pH to 6.6 with 0.1 mol / L sulfuric acid or sodium hydroxide solution. - The degradation reaction was initiated by adding 0.1 g / L of Co-MGC-w catalyst and 0.2 g / L of PMS to a 100 mL round-bottom flask containing a 10 mM aqueous solution. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then injected into a centrifuge tube containing 1 mL of methanol. The concentration of OTC was measured using a UV-visible spectrophotometer (352 nm). The degradation rate of OTC by the Co-MGC-w catalyst was 95.0% within 6 minutes.

[0055] Example 30 (for reaction, see Table 6, entry 3) Set the temperature of the constant temperature magnetic stirring water bath to 25℃ and adjust the initial pH to 6.6 with 0.1 mol / L sulfuric acid or sodium hydroxide solution. - The degradation reaction was initiated by adding 0.1 g / L of Co-MGC-w catalyst and 0.2 g / L of PMS to a 100 mL round-bottom flask containing a 10 mM aqueous solution. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then poured into a centrifuge tube containing 1 mL of methanol. The concentration of OTC was measured using a UV-visible spectrophotometer (352 nm). The degradation rate of OTC over the Co-MGC-w catalyst was 89.0% within 6 minutes.

[0056] Implementation Case 31 (Reaction see Table 6, entry 4) The temperature of a thermostatically stirred water bath was set at 25°C, and the initial pH was adjusted to 6.6 using 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.1 g / L Co-MGC-w catalyst and 0.2 g / L PMS to a 100 mL round-bottom flask containing 50 mL of an aqueous solution of OTC (20 mg / L) and humic acid (HA, 10 mM). At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then poured into a centrifuge tube containing 1 mL of methanol. The OTC concentration was measured using a UV-visible spectrophotometer (352 nm). The degradation rate of OTC over the Co-MGC-w catalyst was 47.0% within 6 minutes.

[0057]

[0058] Implementation Case 32 (Reaction see Table 7, entry 1) The temperature of a thermostatically stirred water bath was set at 25°C, and the initial pH was adjusted to 6.6 using 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.1 g / L Co-MGC-w catalyst and 0.2 g / L PMS to 50 mL of an aqueous solution of OTC (20 mg / L) in a 100 mL round-bottom flask. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then poured into a centrifuge tube containing 1 mL of methanol. The OTC concentration was measured using a UV-visible spectrophotometer (352 nm). The degradation rate of OTC over the Co-MGC-w catalyst was 99.0% within 6 minutes.

[0059] Implementation Case 33 (Reaction see Table 7, entry 2) The temperature of a thermostatically stirred water bath was set at 25°C, and the initial pH was adjusted to 6.6 using 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.1 g / L Co-MGC-w catalyst and 0.2 g / L PMS to 50 mL of an aqueous solution of OTC (20 mg / L) in a 100 mL round-bottom flask. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then poured into a centrifuge tube containing 1 mL of methanol. The OTC concentration was measured using a UV-visible spectrophotometer (352 nm). The degradation rate of OTC over the Co-MGC-w catalyst was 95.0% within 6 minutes.

[0060] Implementation Case 34 (Reaction see Table 7, entry 3) The temperature of a thermostatically stirred water bath was set at 25°C, and the initial pH was adjusted to 6.6 using 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.1 g / L Co-MGC-w catalyst and 0.2 g / L PMS to 50 mL of an aqueous solution of OTC (20 mg / L) in a 100 mL round-bottom flask. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then poured into a centrifuge tube containing 1 mL of methanol. The OTC concentration was measured using a UV-visible spectrophotometer (352 nm). The degradation rate of OTC over the Co-MGC-w catalyst was 90.0% within 6 minutes.

[0061] Implementation Case 35 (Reaction see Table 7, entry 4) The temperature of a thermostatically stirred water bath was set at 25°C, and the initial pH was adjusted to 6.6 using 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.1 g / L Co-MGC-w catalyst and 0.2 g / L PMS to 50 mL of an aqueous solution of 20 mg / L OTC in a 100 mL round-bottom flask. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then poured into a centrifuge tube containing 1 mL of methanol. The OTC concentration was measured using a UV-visible spectrophotometer (352 nm). The degradation rate of OTC over the Co-MGC-w catalyst was 88.5% within 6 minutes.

[0062] Example 36 (for reaction, see Table 7, entry 5) The temperature of a thermostatically stirred water bath was set at 25°C, and the initial pH was adjusted to 6.6 using 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.1 g / L Co-MGC-w catalyst and 0.2 g / L PMS to 50 mL of an aqueous solution of 20 mg / L OTC in a 100 mL round-bottom flask. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then poured into a centrifuge tube containing 1 mL of methanol. The OTC concentration was measured using a UV-visible spectrophotometer (352 nm). The degradation rate of OTC over the Co-MGC-w catalyst was 87.9% within 6 minutes.

[0063]

[0064] Implementation Case 37 (Reaction see Table 8, entry 1) The temperature of a thermostatically stirred water bath was set at 25°C, and the initial pH was adjusted to 6.6 using 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.1 g / L Co-MGC-w catalyst and 0.2 g / L PMS to 50 mL of a 20 mg / L MB aqueous solution in a 100 mL round-bottom flask. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then poured into a centrifuge tube containing 1 mL of methanol. The MB concentration was measured using a UV-visible spectrophotometer (660 nm). The degradation rate of MB over the Co-MGC-w catalyst was 99.3% within 6 minutes.

[0065] Implementation Case 38 (for reactions, see Table 8, entry 2) The temperature of a thermostatically stirred water bath was set at 25°C, and the initial pH was adjusted to 6.6 using 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.1 g / L Co-MGC-w catalyst and 0.2 g / L PMS to 50 mL of a 20 mg / L MR aqueous solution in a 100 mL round-bottom flask. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then poured into a centrifuge tube containing 1 mL of methanol. The MR concentration was measured using a UV-visible spectrophotometer (552 nm). The degradation rate of MR over the Co-MGC-w catalyst was 89.8% within 6 minutes.

[0066] Implementation Case 39 (Reaction see Table 8, entry 3) The temperature of a thermostatically stirred water bath was set at 25°C, and the initial pH was adjusted to 6.6 using 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.1 g / L Co-MGC-w catalyst and 0.2 g / L PMS to 50 mL of RhB (20 mg / L) aqueous solution in a 100 mL round-bottom flask. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then poured into a centrifuge tube containing 1 mL of methanol. The RhB concentration was measured using a UV-visible spectrophotometer (549 nm). The degradation rate of RhB over the Co-MGC-w catalyst was 99.6% within 6 minutes.

[0067] Implementation Case 40 (Reaction see Table 8, entry 4) The temperature of a thermostatically stirred water bath was set at 25°C, and the initial pH was adjusted to 6.6 using 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.1 g / L Co-MGC-w catalyst and 0.2 g / L PMS to 50 mL of a 20 mg / L MO aqueous solution in a 100 mL round-bottom flask. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then poured into a centrifuge tube containing 1 mL of methanol. The MO concentration was measured using a UV-visible spectrophotometer (466 nm). The degradation rate of MO over the Co-MGC-w catalyst was 99.0% within 6 minutes.

[0068] Example 41 (for reaction, see Table 8, entry 5) The temperature of a thermostatically stirred water bath was set at 25°C, and the initial pH was adjusted to 6.6 using 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.1 g / L Co-MGC-w catalyst and 0.2 g / L PMS to a 100 mL round-bottom flask containing 50 mL of a 20 mg / L CIP aqueous solution. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then poured into a centrifuge tube containing 1 mL of methanol. The CIP concentration was measured using a UV-visible spectrophotometer (267 nm). The degradation rate of CIP over the Co-MGC-w catalyst was 99.0% within 6 minutes.

[0069] Example 42 (for reaction, see Table 8, entry 6) The temperature of a thermostatically stirred water bath was set at 25°C, and the initial pH was adjusted to 6.6 using 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.1 g / L Co-MGC-w catalyst and 0.2 g / L PMS to 50 mL of a 20 mg / L CBZ aqueous solution in a 100 mL round-bottom flask. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then poured into a centrifuge tube containing 1 mL of methanol. The CBZ concentration was measured using a UV-visible spectrophotometer (285 nm). The degradation rate of CBZ over the Co-MGC-w catalyst was 99.8% within 6 minutes.

[0070] Implementation Case 43 (Reaction see Table 8, entry 7) The temperature of a thermostatically stirred water bath was set at 25°C, and the initial pH was adjusted to 6.6 using 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.1 g / L Co-MGC-w catalyst and 0.2 g / L PMS to 50 mL of a 20 mg / L NOR aqueous solution in a 100 mL round-bottom flask. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then poured into a centrifuge tube containing 1 mL of methanol. The NOR concentration was measured using a UV-visible spectrophotometer (273 nm). The degradation rate of NOR over the Co-MGC-w catalyst was 93.6% within 6 minutes.

[0071] Example 44 (for reaction, see Table 8, entry 8) The temperature of a thermostatically stirred water bath was set at 25°C, and the initial pH was adjusted to 6.6 using 0.1 mol / L sulfuric acid or sodium hydroxide solution. The degradation reaction was initiated by adding 0.1 g / L Co-MGC-w catalyst and 0.2 g / L PMS to a 100 mL round-bottom flask containing 50 mL of a 20 mg / L SMX aqueous solution. At predetermined time intervals, 1 mL of the reaction solution was extracted and filtered through a 0.22 µm microporous membrane. The filtrate was then poured into a centrifuge tube containing 1 mL of methanol. The SMX concentration was measured using a UV-visible spectrophotometer (265 nm). The degradation rate of SMX over the Co-MGC-w catalyst was 95.0% within 6 minutes.

[0072]

[0073] Example 45 (See Table 9 for the reaction and the effect of different quenchers on OTC degradation) Methanol (MeOH) and tert-butyl alcohol (TBA) are classic free radical quenchers. Specifically, MeOH selectively quenches •OH and SO4•- , while TBA mainly quenches •OH because it reacts with SO4 •- Compared with benzoquinone, its reaction rate with •OH is faster. •- , while curcumin (Cur) and potassium dichromate (K2Cr2O7) can quench singlet oxygen ( 1 O2) and electrons (e - At room temperature, a 100-mL round-bottom flask was filled with 50 mL of an aqueous solution of OTC at a concentration of 20 mg / L and a pH of 6.6. Subsequently, 0.2 g / L of PMS and 0.1 g / L of Co-MGC-w were added to the reactor to initiate the degradation of OTC. At predetermined time intervals, 1 mL samples were withdrawn from the reaction solution. These samples were filtered through a 0.22 µm microporous filter membrane, and the filtrate was poured into a 2-mL centrifuge tube prefilled with 1 mL of methanol. The OTC concentration was then measured using a UV-visible spectrophotometer at a wavelength of 352 nm. The results showed that after 6 minutes of reaction, the degradation rates of OTC over the Co-MGC-w catalyst, quenched by MeOH, TBA, BQ, Cur, and K2Cr2O7, were 83%, 95.8%, 89.5%, 49.9%, and 37%, respectively. The quenching results showed that the inhibitory effect of free radical quencher on the degradation of OTC by Co-MGC-w / PMS system was very small, indicating that the Co-MGC-w catalytic material prepared by microwave pyrolysis of waste glycerol produced free radicals (SO4 •- , OH, O2 •- ) is very small, and the degradation of OTC is almost independent of these three free radicals. The addition of Cur significantly inhibited the degradation rate of OTC to 49.9%. However, considering 1 O2 has low oxidation capacity and poor stability, and its ability to remove pollutants may be overestimated. 1 O2 may play a role in the OTC removal process. When K2Cr2O7 is used as an electron quencher, it can preferentially absorb electrons generated in the reaction system rather than the degradation reaction. After the introduction of K2Cr2O7, the OTC removal rate dropped to 37%, which greatly inhibited the degradation efficiency of OTC and revealed the dominant role of non-radical direct electron transfer in the Co-MGC-w / PMS system. 1 O2 plays a minor role in the degradation of OTC.

[0074]

Claims

1. Application of microwave-assisted biomass waste glycerol-derived carbon aerogel material in the degradation of organic pollutants, characterized in that: Through a convenient and rapid microwave-assisted one-pot solid-state synthesis method, a 300W household microwave oven was used to heat a mixture of glycerol, cobalt nitrate, and potassium hydroxide for 3 minutes to obtain a three-dimensional porous carbon aerogel material. During the microwave reaction, the catalytic material successfully introduced abundant Co-O x species and oxygen vacancies; Compared to traditional pyrolysis methods, microwave pyrolysis achieves rapid carbonization of glycerol. The resulting carbon aerogel material has a three-dimensional porous network structure. This special structure not only significantly increases the specific surface area of the material, but also gives it excellent adsorption properties, providing better adsorption capacity in pollutant degradation reactions. At the same time, metal species can be evenly dispersed on the carrier, providing more active sites. The preparation steps of the above-mentioned carbon aerogel catalytic material are as follows: 1.5 mL of glycerol, 2 mmol of Co(NO3)2•6H2O and 0.50 g of KOH are placed in a crucible and stirred to mix. The crucible is then covered with a lid and placed in a microwave oven. The mixture is pyrolyzed at 300 W for 3 minutes. After cooling to room temperature, the mixture is washed with water / ethanol and dried to obtain the carbon aerogel catalytic material Co-MGC-w. In addition, when only Co(NO3)2•6H2O is replaced by Ni(NO3)2•6H2O or Cu(NO3)2•3H2O under the same reaction conditions, the carbonized catalysts are named Ni-MGC-w and Cu-MGC-w. When KOH was replaced by KHCO3, K2CO3, and NaOH, the catalysts obtained by carbonization were named Co-MGC-w1, Co-MGC-w2, and Co-MGC-w3; The reaction steps for the degradation of organic pollutants by catalyst-activated peroxymonosulfate (PMS) are as follows: 0.1 g / L of catalyst is added to a 100 mL round-bottom flask containing 50 mL of a pH 6.6 aqueous solution containing 20 mg / L of organic pollutants at room temperature and stirred for 15 minutes to reach adsorption equilibrium. Then, PMS with a set concentration of 0.2 g / L is added to the reactor to initiate the degradation process. 1 mL of the reaction solution is extracted at predetermined time intervals and filtered using a 0.22 µm microporous membrane. The filtrate is injected into a centrifuge tube pre-filled with 1 mL of methanol, and the concentration of the organic pollutants is measured at a specific wavelength using a UV-visible spectrophotometer.

2. The use of a microwave-assisted biomass waste glycerol-derived carbon aerogel material in the degradation of organic pollutants according to claim 1, characterized in that: When Co-MGC-w was used as the catalyst, the removal efficiencies of oxytetracycline hydrochloride, ciprofloxacin, carbamazepine, norfloxacin, sulfamethoxazole, methyl red, methylene blue, methyl and rhodamine B could reach 99.0%, 99.0%, 99.8%, 93.6%, 95.0%, 89.8%, 99.3%, 99.0% and 99.6% within 6 min.

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